Flame-retardant resin composition

ABSTRACT

A flame-retardant resin composition comprises 10 to 300 parts by weight of a flame retardant (B) and 1 to 200 parts by weight of an inorganic filler (C) (a glass fiber and/or a glass flake), relative to 100 parts by weight of a base resin (A). The flame retardant (B) comprises a polyphenylene oxide-series resin and/or a polyphenylene sulfide-series resin (B1), a phosphoric ester (B2), and a nitrogen-containing cyclic compound (B3) (for example, a polyphosphate of an amino group-containing triazine compound). The inorganic filler (C) has been treated with a surface-treatment agent or sizing agent containing a novolak epoxy resin. Such a resin composition is useful for obtaining a shaped article which has been inhibited from dripping and to which flame retardancy is highly imparted.

TECHNICAL FIELD

[0001] The present invention relates to a flame-retardant resincomposition having an excellent effect on inhibiting dripping, and ashaped article formed with the composition.

BACKGROUND ART

[0002] Among thermoplastic resins, a polyester-series resin, hasexcellent mechanical and electrical properties, weather resistance,water resistance, and resistance to chemicals and solvents. Therefore,the resin is used as an engineering plastic in various purposes such aselectric or electronic device parts, mechanical device parts andautomotive parts. While, the polyester-series resin is required to haveimproved mechanical properties and to be flame-retardant from theviewpoint of safety as the field of their uses expands. In general,there is known a method for rendering the polyester-series resinflame-retardant by adding a flame retardant composed of ahalogen-containing compound or an antimony-containing compound to theresin. However, the halogen-containing flame retardant is not preferablefor environmental reasons because the flame retardant sometimesgenerates a large amount of a dioxin-series compound on resolutioncaused by combustion. Therefore, there is proposed a method forrendering the polyester-series resin flame-retardant by using apolycarbonate-series resin and a phosphorus-containing compound as ahalogen-free flame retardant.

[0003] Japanese Patent Application Laid-Open No. 168297/1998(JP-10-168297A) discloses a flame-retardant resin composition comprisinga thermoplastic polyester resin, a polycarbonate-series resin, anorganic phosphorus-series flame retardant, and a stabilized redphosphorus. Moreover, Japanese Patent Application Laid-Open No.168295/1998 (JP-10-168295A) discloses a flame-retardant resincomposition comprising a master batch composed of a polyester resin, apolycarbonate resin, a stabilized red phosphorus, and an olefinic resin.

[0004] The halogen-free flame retardant does not comprise harmfulhalogens, however, it is inferior to a halogen-series flame retardant inflame retardancy, so that it is necessary to add a large amount of theflame-retardant. The addition of a large amount of the flame-retardantbrings about bleeding out (blooming) and deterioration in mechanicalproperties of a resin. Therefore, it is difficult to improve flameretardancy, mechanical properties and formability (or moldability).

[0005] On the other hand, there is also known a method for rendering thepolyester-series resin flame-retardant by using a polyphenylene oxideresin and a phosphorus-containing compound. For example, Japanese PatentApplication Laid-Open No. 47056/1985 (JP-60-47056A) discloses athermoplastic resin composition in which a thermoplastic linearpolyester resin, and a flame-retardant comprising a polyphenylene oxideresin, an organic phosphoric ester and a bromine-containing compound areblended. However, this method is not preferable for environmentalreasons because of using a halogen-containing compound.

[0006] Therefore, it is contemplated that flame retardancy is impartedto a polyester resin without using a halogen-containing compound. Forexample, Japanese Patent Application Laid-Open No. 504563/1994(JP-6-504563A) describes a resin composition comprising a polybutyleneterephthalate, a polyphenylene oxide, and a resorcinol diphosphate.However, the resin composition has only approximately V-2 rank based onFlammability test UL-94, and does not have enough flame retardancy.Moreover, burning of the resin composition brings about dripping.

[0007] It is therefore an object of the present invention to provide aflame-retardant resin composition in which dripping has been inhibited,and a shaped article formed with the same.

[0008] It is another object of the present invention to provide aflame-retardant resin composition to which flame retardancy is impartedat a high level by using a halogen-free flame retardant withoutdeteriorating properties of a base resin, and a shaped article formedwith the same.

DISCLOSURE OF THE INVENTION

[0009] The inventors of the present invention made intensive studies toachieve the above objects and finally found that use of a specific flameretardant in combination with an inorganic filler treated with a novolakepoxy resin imparts flame retardancy to a base resin, particularly apolyester-series resin, at a high level and inhibits dripping at a hightemperature. The present invention was accomplished based on the abovefinding.

[0010] That is, the flame-retardant resin composition of the presentinvention comprises a base resin (A), a flame retardant (B) and aninorganic filler (C), in which the flame retardant comprises

[0011] (B1) at least one member selected from the group consisting of apolyphenylene oxide-series resin and a polyphenylene sulfide-seriesresin,

[0012] (B2) a phosphoric ester, and

[0013] (B3) a nitrogen-containing cyclic compound, and the inorganicfiller (C) has been treated with a surface-treatment agent or sizingagent containing a novolak epoxy resin. The inorganic filler (C) maycomprise at least one member selected from the group consisting of aglass fiber and a glass flake. The amount of the surface-treatment agentor sizing agent may be about 0.01 to 5 parts by weight relative to 100parts by weight of the inorganic filler. The base resin may include apolyester-series resin, a polyamide-series resin, an olefinic resin, anacrylic resin, a vinyl-series resin, and others. In particular, in thecase where the base resin is a polyester-series resin (A), the baseresin may comprise a homo- or co-polyester having at least one unitselected from the group consisting of 1,4-cyclohexanedimethyleneterephthalate, a C₂₋₄alkylene terephthalate, and a C₂₋₄ alkylenenaphthalate. The phosphoric ester (B2) may comprise a condensedphosphoric ester, and the nitrogen-containing cyclic compound (B3) maycomprise at least one member selected from the group consisting of apolyphosphate of an amino group-containing triazine compound, and apolyphosphoric acid amide. The flame-retardant resin composition maycontain about 10 to 300 parts by weight of the flame retardant (B) andabout 1 to 200 parts by weight of the inorganic filler (C), relative to100 parts by weight of the base resin (A). The flame retardant (B) maycontain 10 to 500 parts by weight of the component (B1) (thepolyphenylene oxide-series resin and the polyphenylene sulfide-seriesresin) and 0 to 1000 parts by weight of the nitrogen-containing cycliccompound (B3), relative to 100 parts by weight of the phosphoric ester(B2).

[0014] The present invention particularly includes a flame-retardantresin composition comprising at least one polyester-series resin (A)selected from the group consisting of a polybutylene terephthalate, acopolyester containing a butylene terephthalate as a main unit thereof,a polyethylene terephthalate, and a copolyester containing an ethyleneterephthalate as a main unit thereof; a flame retardant (B); and a glassfiber (C); in which the flame retardant (B) comprises the followingcomponents (B1), (B2), and (B3):

[0015] (B1) at least one member selected from the group consisting of apolyphenylene oxide-series resin and a polyphenylene sulfide-seriesresin,

[0016] (B2) a condensed phosphoric ester, and

[0017] (B3) a salt of a polyphosphoric acid having a condensation degreeof 3 to 200 with at least one member selected from the group consistingof melamine and a melamine condensate; and

[0018] the surface of the glass fiber (C) has been treated with 0.05 to3 parts by weight of a surface-treatment agent or sizing agentcontaining a novolak epoxy resin relative to 100 parts by weight of theglass fiber.

[0019] The flame-retardant resin composition may further comprise astyrenic resin (D). Moreover, the flame-retardant resin composition maycomprise at least one flame-retardant auxiliary (or flame-retardantsynergist) selected from the group consisting of a resinousflame-retardant auxiliary (aromatic resin) (E1), and an inorganicflame-retardant auxiliary (E2). As the resinous flame-retardantauxiliary (E1), there may be used at least one aromatic resin selectedfrom the group consisting of a resin of which the main chain or sidechain contains an aromatic ring having at least one group selected froma hydroxyl group and an amino group; a polyarylate-series resin; anaromatic epoxy resin; and a polycarbonate-series resin. As the inorganicflame-retardant auxiliary (E2), there may be used at least one memberselected from the group consisting of a metal borate, a metalhydrogenphosphate, a metal oxide, a metal hydroxide, a metal sulfide,and a red phosphorus.

[0020] Moreover, the flame-retardant resin composition may comprise ahindered phenol-series antioxidant, a phosphorus-containing stabilizer,an inorganic stabilizer, and a compound having a functional groupreactive to an active hydrogen atom (reactive stabilizer), and afluorine-containing resin.

[0021] The present invention also includes a shaped article formed withthe flame-retardant resin composition. The shaped article is useful foran electric or electronic device part, an office automation (OA) devicepart, a household electrical appliance part, an automotive part, or amechanical part or machine element.

BEST MODE FOR CARRYING OUT THE INVENTION

[0022] [Base Resin]

[0023] The base resin is not particularly limited to a specific one, andincludes various thermoplastic resins, thermosetting resins, or others.As the thermoplastic resin constituting the base resin, there may bepreferably used a polyester-series resin, a polyamide-series resin, anolefinic resin, an acrylic resin, a vinyl-series resin, and others.

[0024] (Polyester-Series Resin)

[0025] The polyester-series resin is a homopolyester or copolyesterobtained by, for example, a polycondensation of a dicarboxylic acidcomponent and a diol component, a polycondensation of ahydroxycarboxylic acid or a lactone, or a polycondensation of thesecomponents. The preferred polyester-series resin usually includes asaturated polyester-series resin, in particular an aromatic saturatedpolyester-series resin.

[0026] The dicarboxylic acid component includes, for example, anaromatic dicarboxylic acid [e.g., a dicarboxylic acid having about 8 to16 carbon atoms such as phthalic acid, isophthalic acid, terephthalicacid, a naphthalenedicarboxylic acid (such as2,6-naphthalenedicarboxylic acid), 4,4′-diphenyldicarboxylic acid,4,4′-diphenoxyetherdicarboxylic acid, bis(4-carboxyphenyl)ether,4,4′-diphenylmethanedicarboxylic acid, and4,4′-diphenylketonedicarboxylic acid]. Moreover, the dicarboxylic acidcomponent may be used in combination with an aliphatic dicarboxylic acid(e.g., a dicarboxylic acid having about 4 to 40 carbon atoms such assuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid,azelaic acid, sebacic acid, undecanedicarboxylic acid,dodecanedicarboxylic acid, hexadecanedicarboxylic acid and dimeric acid,preferably a dicarboxylic acid having about 4 to 14 carbon atoms), analicyclic dicarboxylic acid (e.g., a dicarboxylic acid having about 8 to12 carbon atoms such as hexahydrophthalic acid, hexahydroisophthalicacid, hexahydroterephthalic acid, and himic acid), or a derivativethereof (e.g., an ester-formable derivative such as a lower alkyl ester,an aryl ester, and an acid anhydride). These dicarboxylic acidcomponents may be used singly or in combination. Further, if necessary,the dicarboxylic acid component may be used in combination with apolyfunctional carboxylic acid such as trimellitic acid and pyromelliticacid.

[0027] The preferred dicarboxylic acid component includes an aromaticdicarboxylic acid such as terephthalic acid, isophthalic acid, andnaphthalenedicarboxylic acid.

[0028] As the diol component, for example, there are mentioned analiphatic alkylene glycol (e.g., an aliphatic glycol having about 2 to12 carbon atoms such as ethylene glycol, trimethylene glycol, propyleneglycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol,octanediol and decanediol, preferably an aliphatic glycol having about 2to 10 carbon atoms), a polyoxyalkylene glycol [e.g., a glycol having aplurality of oxyalkylene units of which the alkylene group has about 2to 4 carbon atoms, for example, diethylene glycol, dipropylene glycol,ditetramethylene glycol, triethylene glycol, tripropylene glycol, apolytetramethylene glycol], an alicyclic diol (e.g.,1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenolA), and others. Moreover, the diol component may be used in combinationwith an aromatic diol such as hydroquinone, resorcinol, biphenol,2,2-bis(4-hydroxyphenyl)propane,2,2-bis-(4-(2-hydroxyethoxy)phenyl)propane, and xylylene glycol. Thesediol components may be used singly or in combination. Further, ifnecessary, the diol component may be used in combination with a polyolsuch as glycerin, trimethylolpropane, trimethylolethane andpentaerythritol.

[0029] The preferred diol component includes a C₂₋₆ alkylene glycol(e.g., a linear alkylene glycol such as ethylene glycol, trimethyleneglycol, propylene glycol and 1,4-butanediol), a polyoxyalkylene glycolhaving a repeating oxyalkylene unit of about 2 to 4 [a glycol containinga poly(oxy-C₂₋₄alkylene) unit, such as diethylene glycol and apolytetramethylene glycol], and 1,4-cyclohexanedimethanol.

[0030] The hydroxycarboxylic acid includes, for example, ahydroxycarboxylic acid such as hydroxybenzoic acid, hydroxynaphthoicacid, hydroxyphenylacetic acid, glycolic acid and hydroxycaproic acid,or a derivative thereof.

[0031] Exemplified as the lactone is a C₃₋₁₂actone such aspropiolactone, butyrolactone, valerolactone, and caprolactone (e.g.,ε-caprolactone), and others.

[0032] The preferred polyester-series resin includes a homopolyester orcopolyester containing an alkylene arylate unit (such as an alkyleneterephthalate and an alkylene naphthalate) as a main unit (e.g., about50 to 100% by weight, preferably about 75 to 100% by weight) [forexample, a homopolyester such as a polyalkylene terephthalate (e.g., apolyC₂₋₄alkylene terephthalate suchasapoly(1,4-cyclohexanedimethyleneterephthalate) (PCT), a polyethyleneterephthalate (PET), a polypropylene terephthalate (PPT) and apolybutylene terephthalate (PBT)), a polyalkylene naphthalate (e.g., apolyC₂₋₄ alkylene naphthalate such as a polyethylene naphthalate and apolybutylene naphthalate); and a copolyester containing alkyleneterephthalate and/or alkylene naphthalate unit(s) as a main unit (e.g.,not less than 50% by weight)]. The particularly preferredpolyester-series resin includes a polybutylene terephthalate-seriesresin containing a butylene terephthalate unit as a main unit (e.g., apolybutylene terephthalate, and a polybutylene terephthalatecopolyester), a polyethylene terephthalate-series resin containing anethylene terephthalate unit as a main unit (e.g., a polyethyleneterephthalate, and a polyethylene terephthalate copolyester).Incidentally, these polyester-series resins may be used singly or incombination.

[0033] Moreover, in the copolyester, a copolymerizable monomer includesa C₂₋₆alkylene glycol (e.g., a linear alkylene glycol such as ethyleneglycol, propylene glycol and 1,4-butanediol), a polyoxyalkylene glycolwhich has a repeating oxyalkylene unit of about 2 to 4 (e.g., a glycolcomprising a poly(oxy-C₂₋₄alkylene) unit, such as diethylene glycol anda polytetramethylene glycol), a C₆₋₁₂ aliphatic dicarboxylic acid (e.g.,adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid), anaromatic dicarboxylic acid (e.g., phthalic acid, isophthalic acid, adiphenyldicarboxylic acid), a hydroxycarboxylic acid (e.g.,hydroxybenzoic acid, hydroxynaphthoic acid), and others. Incidentally,the polyester-series resin may have not only a linear chain structurebut also a branched chain structure, or crosslinked structure as far asmelt-moldability thereof is not deteriorated. Moreover, thepolyester-series resin may be a liquid crystalline polyester. Such apolyester-series resin may be used singly or in combination.

[0034] The polyester-series resin may be produced by a conventionalmanner, for example, transesterification, direct esterification.

[0035] The number average molecular weight of the polyester-series resinis, for example, about 5×10 to 100×10⁴, preferably about 1×10⁴ to70×10⁴, and more preferably about 1.2×10⁴ to 30×10⁴.

[0036] (Polyamide-Series Resin)

[0037] The polyamide-series resin includes a polyamide derived from adiamine and a dicarboxylic acid; a polyamide obtained from anaminocarboxylic acid, and if necessary in combination with a diamineand/or a dicarboxylic acid; a polyamide derived from a lactam, and ifnecessary in combination with a diamine and/or a dicarboxylic acid. Thepolyamide-series resin also includes a copolyamide derived from at leasttwo different kinds of polyamide constituent components.

[0038] As the diamine, there may be mentioned, for example, an aliphaticdiamine such as trimethylenediamine, tetramethylenediamine,pentamethylenediamine, hexamethylenediamine,2,2,4-trimethylhexamethylenediamine,2,4,4-trimethylhexamethylenediamine, octamethylenediamine andnonamethylenediamine; and an alicyclic diamine such asbis(4-aminocyclohexyl)methane andbis(4-amino-3-methylcyclohexyl)methane. Moreover, the diamine may beused in combination with an aromatic diamine such as phenylenediamineand metaxylylenediamine. These diamines may be used singly or incombination.

[0039] Examples of the dicarboxylic acid are a C₄₋₂₀ aliphaticdicarboxylic acid such as glutaric acid, adipic acid, pimelic acid,suberic acid, azelaic acid, sebacic acid and octadecanoic diacid; adimerized fatty acid (dimeric acid); an alicyclic dicarboxylic acid suchas cyclohexane-1,4-dicarboxylic acid and cyclohexane-1,3-dicarboxylicacid; an aromatic dicarboxylic acid such as phthalic acid, phthalicanhydride, isophthalic acid, terephthalic acid andnaphthalenedicarboxylic acid; and others.

[0040] As the aminocarboxylic acid, there may be mentioned, for example,a C₄₋₂₀aminocarboxylic acid such as aminoheptanoic acid, aminononanoicacid and aminoundecanoic acid. These aminocarboxylic acids may be alsoused singly or in combination.

[0041] As the lactam, for example, there may be mentioned a C₄₋₂₀lactamsuch as butyrolactam, pivalolactam, caprolactam, caprilactam,enantholactam, undecanolactam and dodecalactam. These lactams may bealso used singly or in combination.

[0042] The polyamide-series resin includes an aliphatic polyamide (suchas a nylon 46, a nylon 6, a nylon 66, a nylon 610, a nylon 612, a nylon11 and a nylon 12), a polyamide obtainable from an aromatic dicarboxylicacid (e.g., terephthalic acid and/or isophthalic acid) and an aliphaticdiamine (e.g., hexamethylenediamine, nonamethylenediamine), a polyamideobtainable from both aromatic and aliphatic dicarboxylic acids (e.g.,both terephthalic acid and adipic acid), and an aliphatic diamine (e.g.,hexamethylenediamine), and others. These polyamides may be used singlyor in combination. The preferred polyamide includes a non-aromatic andaliphatic polyamide (e.g., a nylon 6, a nylon 66, a nylon 610, a nylon612, a nylon 11, a nylon 12), a semiaromatic polyamide (e.g., a nylonMXD6, a nylon 9T), a copolymerized semiaromatic polyamide (e.g., a nylon6T/6, a nylon 6T/66, anylon 6T/12, a nylon 6I/6, a nylon 6I/66, a nylon6T/6I, a nylon 6T/6I/6, a nylon 6T/6I/66, a nylon 6T/M5T), and others.These polyamide-series resins may be used singly or in combination.

[0043] (Olefinic Resin)

[0044] As the olefinic resin, for example, there may be mentioned ahomo- or copolymer of an α-olefin such as ethylene, propylene, and1-butene (in particular an α-C₂₋₁₀olefin). The preferred olefinic resinincludes a polyethylene, a polypropylene, an ethylene-propylenecopolymer, and others.

[0045] (Acrylic Resin)

[0046] The acrylic resin includes a homo- or copolymer of a(meth)acrylic monomer [e.g., (meth)acrylic acid, methyl (meth)acrylate,(meth)acrylamide, and (meth)acrylonitrile], or a copolymer of a(meth)acrylic monomer and other copolymerizable monomer.

[0047] (Vinyl-Series Resin)

[0048] The vinyl-series resin includes a homo- or copolymer of avinyl-series monomer [e.g., a vinyl ester such as vinyl acetate, vinylpropionate, vinyl crotonate and vinyl benzoate; a chlorine-containingvinyl monomer (e.g., vinyl chloride, chloroprene); a fluorine-containingvinyl monomer (e.g., fluoroethylene); a vinyl ketone such as methylvinyl ketone and methyl isopropenyl ketone; a vinyl ether such as vinylmethyl ether and vinyl isobutyl ether; and a vinyl amine such asN-vinylcarbazole and N-vinylpyrrolidone], or a copolymer of avinyl-series monomer and other copolymerizable monomer.

[0049] A derivative of the above-mentioned vinyl-series resin (e.g., apolyvinyl alcohol, a polyvinyl acetal such as a polyvinyl formal and apolyvinyl butyral, an ethylene-vinyl acetate copolymer, anethylene-vinyl alcohol copolymer) may be also used.

[0050] The number average molecular weight of the thermoplastic resin isnot particularly limited to a specific one, and is suitably selecteddepending on a kind or application of resin. For example, the numberaverage molecular weight may be selected within the range of about 5×10³to 200×10⁴, preferably about 1×10⁴ to 150×10⁴ and more preferably about1×10⁴ to 100×10⁴ Moreover, in the case where the thermoplastic resin isa polyester-series resin, the number average molecular weight may forexample be about 5×10³ to 100×10⁴ preferably about 1×10⁴ to 70×10⁴, andmore preferably about 1.2×10⁴ to 30×10⁴.

[0051] The above-mentioned thermoplastic resins may be used singly or incombination.

[0052] The preferred thermoplastic resin includes a polyester-seriesresin which may be a liquid crystal polyester, a polyamide-series resin,a vinyl-series resin, or others, and particularly includes apolyester-series resin (e.g., a PBT-series resin, a PET-series resin).

[0053] [Flame Retardant (B)]

[0054] According to the present invention, the flame retardant (B)comprising a polyphenylene oxide-series resin and/or polyphenylenesulfide-series resin (B1), a phosphoric ester (B2), and anitrogen-containing cyclic compound (B3) imparts high flame retardancyto the base resin without deteriorating properties of the base resin.(B1) Polyphenylene oxide-series resin, polyphenylene sulfide-seriesresin

[0055] The polyphenylene oxide-series resin (polyphenylene ether-seriesresin) includes a homopolymer and a copolymer. As the homopolymer, theremay be mentioned a poly(mono-, di- or triC₁₋₆alkyl-phenylene) oxide suchas a poly(2,6-dimethyl-1,4-phenylene) oxide, apoly(2,5-dimethyl-1,4-phenylene) oxide, apoly(2,5-diethyl-1,4-phenylene) oxide, apoly(2-methyl-6-ethyl-1,4-phenylene) oxide, apoly(2,6-di-n-propyl-1,4-phenylene)oxide, apoly(2-ethyl-6-isopropyl-1,4-phenylene)oxide, apoly(2-methyl-6-methoxy-1,4-phenylene)oxide, apoly(2-methyl-6-hydroxyethyl-1,4-phenylene)oxide, apoly(2,3,6-trimethyl-1,4-phenylene) oxide, apoly(2,6-diphenyl-1,4-phenylene)oxide, and apoly(2-methyl-6-phenyl-1,4-phenylene)oxide; a poly(mono- ordiC₆₋₂₀aryl-phenylene)oxide; and apoly(monoC₁₋₆alkyl-monoC₆₋₂₀aryl-phenylene)oxide.

[0056] As the copolymer of a polyphenylene oxide, there may bementioned: a copolymer having not less than two monomer unitsconstituting the above-mentioned homopolymers (e.g., a random copolymerhaving 2,6-dimethyl-1,4-phenylene oxide unit and2,3,6-trimethyl-1,4-phenylene oxide unit); a modified polyphenyleneoxide copolymer comprising an alkylphenol-modified benzene formaldehyderesin block which is obtainable by a reaction of an alkylphenol (such ascresol and p-tert-butylphenol) with a benzene formaldehyde resin (acondensation product of a benzene ring-containing compound andformaldehyde, such as a phenol resin) or alkylbenzene formaldehyderesin, and a polyphenylene oxide block as the main structure; a modifiedgraft copolymer in which a styrenic polymer is grafted to apolyphenylene oxide or a copolymer thereof; and others.

[0057] These polyphenylene oxide-series resins may be used singly or incombination.

[0058] The polyphenylene sulfide-series resin (polyphenylenethioether-series resin) includes a homopolymer or copolymer having apolyphenylene sulfide backbone, —(Ar—S—)— (wherein Ar represents aphenylene group). As the phenylene group (—Ar—), there may be mentioned,for example, p-phenylene group, m-phenylene group, o-phenylene group-, asubstituted phenylene group (e.g., an alkylphenylene group havingsubstituent(s) such as a C₁₋₅alkyl group, an arylphenylene group havingsubstituent(s) such as phenyl group), p,p′-diphenylenesulfone group,p,p′-biphenylene group, p,p′-diphenylene ether group, andp,p′-diphenylenecarbonyl group. The polyphenylene sulfide-series resinmay be a homopolymer obtained from a homogeneous repeating unit amongthe phenylene sulfide groups comprising such a phenylene group, or inview of workability of the composition, the polyphenylene sulfide-seriesresin may be a copolymer containing a heterogeneous repeating unit amongthe phenylene sulfide groups comprising such a phenylene group.

[0059] As the homopolymer, a substantially linear polymer comprisingp-phenylene sulfide group as a repeating unit is preferably used. Thecopolymer may be obtained from two or more different kinds of phenylenesulfide groups among the phenylene sulfide groups. Among them, acopolymer comprising p-phenylene sulfide group as a main repeating unitin combination with m-phenylene sulfide group is preferred as thecopolymer. From the viewpoint of physical properties such as heatresistance, moldability, and mechanical property, a substantially linearcopolymer comprising not less than 60 mol % (preferably 70 mol %) ofp-phenylene sulfide group is particularly preferred.

[0060] The polyphenylene sulfide-series resin may be a polymer obtainedby allowing a relatively low molecular weight of a linear polymer tocrosslink with oxidation or heating for increasing the melt viscosity ofthe polymer thereby improving molding processability(mold-processability), or a high molecular weight polymer having asubstantially linear structure which polymer is obtained by condensationpolymerization from a monomer mainly comprising a bifunctional monomer.From the viewpoint of physical properties of the resultant shapedarticle, a polymer having a substantially linear structure, which isobtained by condensation polymerization, is more preferred. Moreover, asthe polyphenylene sulfide resin, in addition to the above-mentionedpolymer, a branched or crosslinked polyphenylene sulfide resin obtainedby a polymerization of the monomer in combination with a monomer havingnot less than three of functional groups, or a resin compositionobtained by blending the resin to the above-mentioned linear polymer maybe also used.

[0061] As the polyphenylene sulfide-series resin, there may be used apolyphenylene sulfide (e.g., a poly-1,4-phenylene sulfide) or apolybiphenylene sulfide (PBPS), in addition a polyphenylene sulfideketone (PPSK), a polybiphenylene sulfide sulfone (PPSS), or others. Thepolyphenylene sulfide-series resin may be used singly or in combination.

[0062] These polyphenylene oxide-series resins and these polyphenylenesulfide-series resins may be used singly or in combination.

[0063] (B2) Phosphoric Ester

[0064] The phosphoric ester includes a monomeric phosphoric ester (aphosphoric ester, a phosphorous ester, a hypophosphorous ester), apolymeric phosphoric ester, and others.

[0065] As the phosphoric ester, there may be mentioned an aliphaticphosphoric ester [for example, a triC₁₋₁₀alkyl phosphate such astrimethyl phosphate, triethyl phosphate, tripropyl phosphate,triisopropyl phosphate, tributyl phosphate, triisobutyl phosphate, andpentaerythritol phosphate [e.g., NH-1197 (manufactured by Great LakesChemical Corporation), a bicyclophosphoric ester described in JapanesePatent Application Laid-Open No. 106889/2001 (JP-2001-106889A)]; adiC₁₋₁₀alkyl phosphate and monoC₁₋₁₀alkyl phosphate corresponding to theabove-mentioned phosphoric triester], an aromatic phosphoric ester [forexample, a triC₆₋₂₀aryl phosphate such as triphenyl phosphate, tricresylphosphate, trixylyl phosphate, diphenyl cresyl phosphate,tri(isopropylphenyl) phosphate and diphenyl ethylcresyl phosphate], analiphatic-aromatic phosphoric ester [e.g., methyl diphenyl phosphate,phenyl diethyl phosphate, a polyphenol (a cyclic alkylene glycolphosphate) [e.g., resorcinol bis(neopentylene glycol phosphate),hydroquinone bis (neopentylene glycol phosphate), biphenolbis(neopentylene glycol phosphate), bisphenol-A bis(neopentylene glycolphosphate)], a spiro ring-containing aromatic phosphoric ester (e.g.,diphenyl pentaerythritol diphosphate, dicresyl pentaerythritoldiphosphate, dixylyl pentaerythritol diphosphate)], and others.

[0066] The phosphite (or phosphorous ester) includes a variety ofphosphorous esters, for example, an aromatic phosphorous ester (e.g., atriC₆₋₂₀aryl phosphate in which aryl groups are phenyl, cresyl, xylylgroup, or other group), an aliphatic phosphorous ester (e.g., atriC₁₋₁₀alkyl phosphite in which alkyl groups are methyl, ethyl, propyl,isopropyl, butyl, isobutyl, or other groups; a di- or monoC₁₋₁₀alkylphosphate corresponding to the above-mentioned trialkyl phosphate), anorganic phosphorous ester [for example, a diC₁₋₆alkyl ester of a C₁₋₆alkylphosphorous acid (an ester of a spiro ring-containingalkylphosphorous acid such as pentaerythritol bis(methylphosphonate),pentaerythritol bis(ethylphosphonate), pentaerythritolbis(propylphosphonate), and pentaerythritol bis(butylphosphonate)); adiester of an alkylphosphorous acid such as a diC₆₋₁₀aryl ester of aC₁₋₆alkylphosphorous acid and a C₁₋₆alkylC₆₋₁₀aryl ester of aC₁₋₆alkylphosphorous acid, of which the alkyl group is theabove-exemplified alkyl group; a diester of C₆₋₁₀aryl-phosphorous acidcorresponding to the above-mentioned diester of an alkylphosphorous acid(e.g., an ester of a spiro ring-containig arylphosphorous acid such aspentaerythritoi bis(phenylphosphonate) and pentaerythritolbis(tolylphosphonate)); a C₆₋₁₀arylphosphorous monoester (e.g.,10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide); aphosphonocarboxylate (a phosphonocarboxylic triester such as a C₁₋₄alkoxycarbonyloxyC₁₋₄alkylphosphorous diester corresponding to theabove-mentioned alkylphosphorous diester, e.g., dimethylmethoxycarbonylmethylphosphonate)]. Moreover, the phosphite (phosphorousester) also includes a metal salt (for example, a Ca, Mg, Zn, Ba, or Alsalt) of a (cyclic) phosphorous monoester, or phosphonocarboxylic acid,each of which may have substituent(s) such as an alkyl group or an arylgroup (e.g., a monoalkyl alkylphosphite, a monoaryl alkylphosphite, amonoalkyl arylphosphite, a monoaryl arylphosphite). For example, thedetails about representative compounds of such a metal salt of anorganic phosphorous ester may be referred to Japanese Patent ApplicationLaid-Open No. 22866/1988 (JP-63-22866A), Japanese Patent ApplicationLaid-Open No. 226891/1989 (JP-1-226891A), Japanese Patent ApplicationLaid-Open No. 234893/1992 (JP-4-234893A), Japanese Patent ApplicationLaid-Open No. 245659/1996 (JP-8-245659A), and Japanese PatentApplication Laid-Open No. 272759/1997 (JP-9-272759A).

[0067] The hypophosphite (hypophosphorous ester) includes ahypophosphorous ester which may be substituted (mono- or disubstituted)with an alkyl group(s) such as a C₁₋₄alkyl group or an aryl group(s)such as a C₆₋₁₀aryl group (e.g., a C₁₋₆alkyl hypophosphite such asmethyl hypophosphite, a C₆₋₁₀aryl hypophosphite such as phenylhypophosphite, and a cyclic hypophosphorous ester such as9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a 10-C₁₋₃₀alkylorC₆₋₂₀aryl-substituted-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide).Moreover, the hypophosphite also includes an ester of aphosphinicocarboxylic acid which may have a substituent such as an alkylgroup or an aryl group (e.g., an ester of 3-methylphosphinicopropionicacid, an ester of 3-phenylphosphinicopropionic acid), and a homo- orcopolymer thereof.

[0068] As the polymeric phosphoric ester (or phosphate), there may beused a condensed phosphate. The condensed phosphate includes a condensedphosphate having an aromatic ring, and may for example have a structuralunit represented by the following formula (1):

[0069] wherein R¹ to R⁴ represent an aryl group which may have asubstituent, Z¹ represents a bifunctional aromatic group, and “p”denotes an integer of not less than 1.

[0070] In the formula (1), the aryl groups represented by the R¹ to R⁴include a C₆₋₂₀aryl group (e.g., phenyl group, and naphthyl group), andthe substituent of the aryl group includes an alkyl group such as methylgroup and ethyl group. Moreover, the bifunctional aromatic groupincludes an arylene group (e.g., a C₆₋₂₀arylene group such as phenylenegroup and naphthylene group), a biphenylene group and a bisphenolresidue (e.g., a bisphenol A residue, a bisphenol D residue, and abisphenol AD residue), and others. The number “p” denotes an integer ofnot less than 1, preferably an integer of 1 to 100, and particularlypreferably an integer of 1 to 30.

[0071] The condensate represented by the formula (1) includes, forexample, a resorcinol phosphate [e.g., resorcinol bis(diphenylphosphate), resorcinol bis(dicresyl phosphate), resorcinol bis(dixylylphosphate)], a hydroquinone phosphate [e.g., hydroquinone bis(diphenylphosphate), hydroquinone bis(dicresyl phosphate), and hydroquinonebis(dixylyl phosphate)], a biphenol phosphate [e.g., biphenolbis(diphenyl phosphate), biphenol bis(dicresyl phosphate), and biphenolbis(dixylyl phosphate)], a bisphenol phosphate [e.g., bisphenol-Abis(diphenyl phosphate), bisphenol-A bis(dicresyl phosphate), andbisphenol-A bis(dixylyl phosphate)], and others.

[0072] Moreover, the polymeric phosphoric ester may be a phosphoricester of a polymer having a hydroxyl group (such as a phenolic resin).Such a phosphoric ester of a polymer includes, for example, a polymerhaving a structural unit represented by the following formula (2):

[0073] wherein R⁵ and R⁶ represent an aryl group.

[0074] The aryl group includes the above-exemplified aryl group (aC₆₋₂₀aryl group, in particular phenyl group) and a substituted arylgroup (an alkyl-substituted aryl group).

[0075] Moreover, the phosphoric ester also includes anitrogen-containing phosphoric ester having a partial structure of thephosphoric ester [for example, a phosphazene (a chain and/or cyclicphenoxyphosphazene; an aryloxyphosphazene modified with a polyhydricphenol (a polyhydroxyphenol such as hydroquinone, resorcinol, andphloroglucin; a biphenol, and a bisphenol (e.g., bisphenol A)), e.g.,phenoxyphosphazene, tolyloxyphosphazene, and tolyloxyphenoxyphosphazene;and a phosphoric ester amide (e.g., compounds described in JapanesePatent Application Laid-Open No. 226547/2002 (JP-2002-226547A), JapanesePatent Application Laid-Open No. 354684/2001 (JP-2001-354684A), JapanesePatent Application Laid-Open No. 327834/2000 (JP-2000-327834A), JapanesePatent Application Laid-Open No. 139823/2001 (JP-2001-139823A), JapanesePatent Application Laid-Open No. 154277/2000 (JP-2000-154277A), JapanesePatent Application Laid-Open No. 175985/1998 (JP-10-175985A), JapanesePatent Application Laid-Open No. 59888/1996 (JP-8-59888A), JapanesePatent Application Laid-Open No. 2353/1988 (JP-63-2353A), JapanesePatent Application Laid-Open No. 19719/1979 (JP-54-19719A), andothers)].

[0076] The preferred phosphoric ester amide includes condensedphosphoric ester amides having high molecular weight. As such aphosphoric ester amide, for example, there may be mentioned anN-(diaryloxyphosphinyl)-substituted alkyleneamine [e.g.,N,N′-bis(diphenoxyphosphinyl)piperazine,N,N′-bis(ditolyloxyphosphinyl)piperazine,N,N′-bis(dixylyloxyphosphinyl)piperazine, N,N′-bis(di- ortrimethylphenyloxyphosphinyl)piperazinel; a bis- totetrakis[(diaryloxyphosphinyl)amino]-substituted aromatic compound[e.g., 1,3- or 1,4-bis[(diphenoxyphosphinyl)amino]benzene, 1,3- or1,4-bis[(ditolyloxyphosphinyl)amino]benzene, 1,3- or1,4-bis[(dixylyloxyphosphinyl)amino]benzene, 1,3- or 1,4-bis[(di- ortrimethylphenyloxyphosphinyl)amino]benzene, 1,3- or 1, 4-bis[(diphenoxyphosphinyl)aminomethyl]benzene, 1,3- or1,4-bis[(ditolyloxyphosphinyl)aminomethyl]benzene, 1,3- or1,4-bis[(dixylyloxyphosphinyl)aminomethyl]benzene, 1,3-or 1,4-bis[(di-or trimethylphenyloxyphosphinyl)aminomethyl]benzene]; an N-(cyclicalkylenedioxyphosphinyl)-substituted alkyleneamine [e.g.,N,N′-bis(neopentylenedioxyphosphinyl)piperazine];a bis totetrakis[(cyclic alkylenedioxyphosphinyl)amino]-substituted aromaticcompound [e.g., 1,3- or1,4-bis[(neopentylenedioxyphosphinyl)amino]benzene, 1,3- or1,4-bis[(neopentylenedioxyphosphinyl)aminomethyl]benzene]; an N-(cyclicarylenedioxyphosphinyl)-substituted alkyleneamine [e.g.,N,N′-bis(phenylene-1,2-dioxyphosphinyl)piperazine, 1,3- or1,4-bis[(biphenylene-2,2′-dioxyphosphinyl)aminomethyl]piperazine]; a bisto tetrakis[(cyclic arylenedioxyphosphinyl)amino]-substituted aromaticcompound (e.g., 1,3- or1,4-bis[(phenylene-1,2-dioxyphosphinyl)amino]benzene, 1,3- or1,4-bis[(biphenylene-2,2′-dioxyphosphinyl)aminomethyl]benzene}, and a3,9-bis(N-substitutedamino)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]-undecane-3,9-dioxide[e.g., a spiro ring-containing phosphoric ester amide of which theN-substituted amino group is a dialkylamino group (e.g., diethylaminogroup), a cyclic amino group (e.g., piperidino group, pipecolino group,dimethylpiperidino group, morpholino group), an arylamino group (e.g.,phenylamino group), or an alkylarylamino group (e.g., methylphenylaminogroup)]. Such a phosphoric ester amide is commercially available astrade name “PHOSPHORIC ESTER AMIDE FLAME RETARDANT SP SERIES (e.g.,SP-601, SP-670, SP-703, SP-720)” (manufactured by Shikoku ChemicalsCorp.).

[0077] These phosphoric esters may be used singly or in combination.

[0078] The preferred phosphoric ester includes an aromatic phosphoricester and a condensed phosphoric ester, and particularly a condensedphosphoric ester. (B3) Nitrogen-containing cyclic compound Thenitrogen-containing cyclic compound includes a nitrogen-containingcyclic compound or a salt thereof, and others.

[0079] The nitrogen-containing cyclic compound includes a heterocycliccompound having at least one amino group, and at least one nitrogen atomas a hetero atom of a heterocycle. The heterocycle may have other heteroatom(s) such as sulfur and oxygen other than nitrogen. Such anitrogen-containing heterocycle includes a 5- or 6-membered unsaturatednitrogen-containing heterocycle having a plurality of nitrogen atoms asconstituent atoms thereof, for example, imidazole, thiadiazole,thiadiazoline, furazan, triazole, thiadiazine, pyrazine, pyrimidine,pyridazine, triazine, and purine. Among such nitrogen-containing rings,a 5- or 6-membered unsaturated nitrogen-containing ring having aplurality of nitrogen atoms as constituent atoms thereof is preferred,and in particular, triazole and triazine are preferred.

[0080] As the triazole compound, there may be mentioned a 1,2,3-triazole(e.g., a 1H-1,2,3-triazole; a 2H-1,2,3-triazole), a 1,2,4-triazole(e.g., a 1H-1,2,4-triazole such as guanazole; a 4H-1,2,4-triazole suchas guanazine), and the like. The arbitrary atom constituting a triazolering (particular carbon atom) has an amino group(s) as substituent(s).The number of the amino group is, for example, about 1 to 3, andpreferably about 1 to 2.

[0081] The triazine compound includes a variety of triazines: a1,3,5-triazine [for example, a melamine or a derivative thereof such asmelamine, a substituted melamine (e.g., an alkylmelamine such as 2-methylmelamine, guanylmelamine), a condensation product of a melamine(melamine condensate) (e.g., melam, melem, melon), and a copolycondensedresin of a melamine (e.g., a melamine-formaldehyde resin, aphenol-melamine resin, a benzoguanamine-melamine resin, an aromaticpolyamine-melamine resin); a hydroxyl group-containing 1,3,5-triazine(e.g., cyanuric acid, and isocyanuric acid); a cyanuric amide (e.g.,ammeline, ammelide); a guanamine or a derivative thereof (e.g.,guanamine, methylguanamine, acetoguanamine, benzoguanamine,succinoguanamine and CTU-guanamine)], an amino group-containing1,2,3-triazine (e.g., 1,2,3-triazine having an-amino group(s) assubstituent(s) at 5-position, 4,5-positions or 4,5,6-positions,4-amino-benzo-1,2,3-triazine), and an amino group-containing1,2,4-triazine (e.g., 1,2,4-triazine having an amino group(s) assubstituent(s) at 3-position, 5-position or 3,5-positions). Thearbitrary atom constituting a triazine ring (particularly carbon atom)has an amino group(s) as substituent(s). The number of the amino groupis, for example, about 1 to 4, preferably about 1 to 3, and morepreferably about 2 to 3. Incidentally, the hydroxyl group-containingtriazine may form a salt with other triazine (particularly an aminogroup-containing triazine, e.g., melamine, and a melamine condensate).

[0082] The preferred nitrogen-containing cyclic compound includes theamino group-containing triazine compound, particularly the aminogroup-containing 1,3,5-triazine (e.g., melamine, a melamine condensate,particularly melam and melem).

[0083] Examples of the salt of the nitrogen-containing cyclic compoundinclude a salt of the nitrogen-containing cyclic compound(nitrogen-containing cyclic compound having an amino group) with anoxygen acid, an organic phosphoric acid, or an organic sulfonic acid.

[0084] (i) Salt of Nitrogen-Containing Cyclic Compound with Oxygen Acid

[0085] In the salt with an oxygen acid, the nitrogen-containing cycliccompound (nitrogen-containing cyclic compound having an amino group) mayform a salt with an oxygen acid at a nitrogen atom site (imino group)constituting a ring. It is usually preferred to form a salt of an oxygenacid with at least one amino group which is a substituent of a ring ofthe cyclic compound. In the case having a plurality of amino groups, allamino groups may form a salt with the oxygen acid. Moreover, a pluralityof nitrogen-containing compounds which are the same or different kind(the above-mentioned nitrogen-containing cyclic compound, or othernitrogen-containing compound which contains an amino group) may form asalt with one polyphosphoric acid to form a double salt (or complexsalt) of a polyacid.

[0086] The oxygen acid includes nitric acid, a chloric acid (such asperchloric acid, chloric acid, chlorous acid, and hypochlorous acid), aphosphoric acid [e.g., a phosphoric acid (non-condensed phosphoric acid)and a polyphosphoric acid (condensed phosphoric acid)], a sulfuric acid(e.g., a non-condensed sulfuric acid such as peroxymonosulfuric acid,sulfuric acid, and sulfurous acid; a condensed sulfuric acid such asperoxydisulfuric acid, and pyrosulfuric acid), a boric acid (e.g., anon-condensed boric acid such as orthoboric acid, and metaboric acid; acondensed boric acid such as tetraboric acid, and boric anhydride), anantimonic acid, a molybdic acid, and a tungstic acid. Among others, apolyphosphoric acid, a sulfuric acid, and a boric acid are preferred.

[0087] The polyphosphoric acid also includes a condensed phosphoric acidrepresented by the following formula (3):

[0088] wherein “q” denotes an integer of not less than 2.

[0089] In the formula, “q” represents a condensation degree of thepolyphosphoric acid. The number “q” may just be an integer of not lessthan 2, and is preferably an integer of 2 to 2400, more-preferably aninteger of 3 to 200, and particularly an integer of 3 to 100.

[0090] Moreover, the polyphosphoric acid also includes apolymetaphosphoric acid (HPO₃)n (in the formula, “n” denotes an integerof not less than 2), hypophosphoric acid, phosphoric anhydride(diphosphorus pentoxide), and others.

[0091] Incidentally, in a polyphosphoric acid having a plurality ofsalifiable sites, at least part of sites may form a partial salt withother amino group-containing compound such as an amine or a urea (e.g.,a partial salt such as an ammonium polyphosphate and a ureapolyphosphate).

[0092] The salt of the oxygen acid includes, to take a melamine salt asan example, a non-condensed phosphate such as melamine orthophosphate; apolyphosphate such as melamine pyrophosphate; a non-condensed sulfatesuch as a melamine sulfate (e.g., melamine sulfate, dimelamine sulfate,guanylmelamine sulfate), and a melamine sulfite corresponding to themelamine sulfate; a condensed sulfate such as a melamine pyrosulfate(e.g., melamine pyrosulfate, dimelamine pyrosulfate); a non-condensedborate such as a melamine orthoborate (e.g., a mono- to trimelamineorthoborate), and a metaborate corresponding to the orthoborate; acondensed borate such as anhydrous melamine borate and melaminetetraborate; and others.

[0093] Moreover, the salt of the oxygen acid also includes a salt suchas a melam salt, melem salt, melon salt, guanamine salt, acetoguanaminesalt and benzoguanamine salt corresponding to the melamine salt of theoxygen acid, and a double salt (or complex salt) such as amelamine-melam double salt, a melamine-melam-melon double salt and amelam-melem double salt, and others.

[0094] Among the salts with oxygen acids, a salt of anitrogen-containing cyclic compound (in particular a nitrogen-containingcyclic compound having an amino group) with a polyphosphoric acid ispreferred. Examples of such a polyphosphate of a nitrogen-containingcyclic compound include a polyphosphate of an amino group-containingtriazine compound [e.g., a melamine pyrophosphate (melaminepyrophosphate, dimelamine pyrophosphate), a melamine polyphosphate (suchas a triphosphate and a tetraphosphate) corresponding to the melaminepyrophosphate; a melem salt, melam salt, melon salt or guanamine saltcorresponding to the melamine polyphosphatel. Moreover, a triazole saltcorresponding to the triazine salt may be also used. In particular, itis preferred to use a salt of at least one member selected from melamineand a melamine condensate with a polyphosphoric acid (particularly apolyphosphoric acid having a condensation degree of 3 to 100). Moreover,the polyphosphate also includes a melamine-melam-melem double salt of apolyphosphoric acid, a melamine-melam-melem double salt ofmetaphosphoric acid, and others.

[0095] Further, the nitrogen-containing cyclic compound may contain asulfur atom derived from sulfuric acid. Such a nitrogen-containingcyclic compound includes a salt of a nitrogen-containing cyclic compound(particularly melamine, a melamine condensate) with a polyacidcontaining an atom such as a sulfur atom and an oxygen atom in additionto a phosphorus atom (e.g., a polyacid, having a phosphatosulfuric acidgroup, formed from phosphorus, sulfur and oxygen; a mixture of thispolyacid and a polyphosphoric acid and/or pyrosulfuric acid; a mixtureof a polyphosphoric acid and pyrosulfuric acid), a salt of thenitrogen-containing cyclic compound with a mixture of a phosphoric acidor a polyphosphoric acid and a sulfuric acid, and also includes amelamine-melammelem double salt. The nitrogen-containing cyclic compoundcontaining a sulfur atom derived from a sulfuric acid may for example beobtained by mixing a nitrogen-containing cyclic compound, a phosphoricacid or polyphosphoric acid, and a sulfuric acid, and calcining themixture, or may be obtained by mixing a nitrogen-containing cycliccompound and the polyacid, and calcining the mixture. The detailed thesepolyphosphates (including double salts) which may contain a sulfur atomcan be referred to Japanese Patent Application Laid-Open No. 306081/1998(JP-10-306081A), Japanese Patent Application Laid-Open No. 306082/1998(JP-10-306082A), and others.

[0096] These polyphosphates may be treated with the use of asurface-modifying agent such as an epoxy-series compound, asilane-series compound, a titanate-series compound, and achromium-series compound. The use of the polyphosphate not only impartshigh flame retardancy to the polyester-series resin, but also causes nopossibility of staining (or coloring) in the resin composition.

[0097] The proportion of the nitrogen-containing cyclic compoundrelative to the polyphosphoric acid is not particularly limited to aspecific one, and the former/the latter (molar ratio) is, for example,about 1/20 to 20/1, preferably about 1/10 to 10/1 (e.g., about 1/5 to10/1), and particularly about 1/2 to 8/1. The equivalence ratio of anamino group contained in the nitrogen-containing cyclic compoundrelative to a salifiable site of the polyphosphoric acid is also notparticularly limited to a specific one, and is, for example, about 10/1to 1/2, preferably about 5/1 to 1/1, and particularly about 4/1 to 1/1.

[0098] (ii) Salt of Nitrogen-Containing Cyclic Compound with OrganicPhosphoric Acid

[0099] The organic phosphoric acid includes a partial ester of anon-condensed phosphoric acid [e.g., peroxy acid, orthophosphoric acid,metaphosphoric acid, phosphorous acid (phosphonic acid), orhypophosphorous acid (phosphinic acid)], and phosphonic acid orphosphinic acid each having an organic group as a substituent. It issufficient that the organic phosphoric acid may just have at least onesite salifiable with the nitrogen-containing cyclic compound(particularly a nitrogen-containing cyclic compound having an aminogroup).

[0100] The organic phosphoric acid may form a salt with thenitrogen-containing cyclic compound at part or whole of salifiablesite(s), and both of the salts may be used. Such an organic phosphateincludes, to take a melamine salt as an example, a melamine salt of anorganic phosphoric ester (e.g., salt of pentaerythritol bisphosphatewith melamine, salt of pentaerythritol bisphosphate with dimelamine); amelamine salt of a C₁₋₆alkyl-substituted phosphorous acid; a melaminesalt of a mono- or diphosphorous ester of a C₁₋₆aliphatic diol (e.g.,salt of 1-hydroxyethylidene-1,1-diphosphorous acid with dimelamine, saltof 1-hydroxyethylidene-1,1-diphosphorous acid with tetramelamine);tetramelamine salt of nitrilotris(methylphosphonic acid) (tetramelaminesalt of [nitrilotris(methylene)]trisphosphonic acid), hexamelamine saltof nitrilotris(methylphosphonic acid) (hexamelamine salt of[nitrilotris(methylene)]trisphosphonic acid) ; amelamine salt of aC₆₋₁₀arylphosphorous acid, (melamine salt of phenylphosphorous acid,dimelamine salt of phenylphosphorous acid), a melamine salt of aphosphinicocarboxylic acid (a melamine salt of anarylphosphinicocarboxylic acid, such as melamine salt of3-(phenylphosphinico)propionic acid and dimelamine salt of3-(phenylphosphinico)propionic acid); and others. Moreover, there maybealso used a double salt corresponding to the melamine salt, such as saltof pentaerythritol bisphosphate with melamine and melem.

[0101] (iii) Salt of Nitrogen-Containing Cyclic Compound with OrganicSulfonic Acid

[0102] Examples of the salt of the nitrogen-containing cyclic compoundwith an organic sulfonic acid include a salt of a melamine (e.g.,melamine, melam, melem) with an organic sulfonic acid [e.g., aC₁₋₁₀alkylsulfonic acid (such as methanesulfonic acid, ethanesulfonicacid, and ethanedisulfonic acid), a C₆₋₂₀arylsulfonic acid (such asbenzenesulfonic acid, and toluenesulfonic acid)], a double salt thereof,and others.

[0103] [Proportion of Flame Retardant]

[0104] By using the flame retardant of the present invention incombination with at least one member selected from a polyphenyleneoxide-series resin and a polyphenylene sulfide-series resin, aphosphoric ester, and a nitrogen-containing cyclic compound, the flameretardant imparts high flame retardancy to the base resin withoutdeteriorating properties of the base resin (e.g., without possibility ofstaining or bleeding out), and the amount to be added of the flameretardant can be reduced. The proportion of the flame retardant relativeto the base resin is about 10 to 300 parts by weight, preferably about20 to 250 parts by weight, and more preferably about 30 to 200 parts byweight, relative to 100 parts by weight of the base resin.

[0105] The proportions of each component in the flame retardant may besuitably selected within the range that flame retardancy can be impartedto a resin. For example, the proportion of the polyphenyleneoxide-series resin and/or polyphenylene sulfide-series resin (B1) isabout 5 to 500 parts by weight, preferably about 10 to 450 parts byweight (e.g., about 30 to 450 parts by weight), and more preferablyabout 15 to 400 parts by weight (e.g., about 50 to 400 parts by weight),relative to 100 parts by weight of the phosphoric ester (B2). Theproportion of the nitrogen-containing cyclic compound (B3) is, forexample, about 0 to 1000 parts by weight, about 0 to 700 parts byweight, and more preferably about 0 to 500 parts by weight, relative to100 parts by weight of the phosphoric ester(B2).

[0106] [Inorganic Filler (C)]

[0107] In the present invention, the combination use of the flameretardant (B), and the inorganic filler (C) treated with asurface-treatment agent or sizing agent containing a novolak epoxy resininhibits dripping from a resin composition at a high temperature, andensures high flame retardancy.

[0108] The inorganic filler includes a fibrous filler such as a glassfiber, an asbestos fiber, a carbon fiber, a silica fiber, asilica-alumina fiber, a zirconia fiber, a potassium titanate fiber, anda metal fiber (e.g., a chopped strand, a roving); and a non-fibrousfiller such as a plate-like filler (e.g., a glass flake, a mica, agraphite, a variety of metal foil), and a particulate filler [forexample, a carbon black, a silica, a powder of quartz, a glass bead, aglass powder, a milled fiber (such as a milled glass fiber), a silicate(e.g., a calcium silicate, an aluminum silicate, a kaolin, a talc, aclay, a diatomite, a wollastonite); a metal oxide (e.g., an iron oxide,a titanium oxide, a zinc oxide, an alumina); a metal carbonate (e.g., acalcium carbonate, a magnesium carbonate); a metal sulfate (e.g., acalcium sulfate, a barium sulfate); and a metal powder (such as asilicon carbide)].

[0109] In the fibrous filler, the fiber length of the chopped strand is,for example, about 10 to 100000 μm, preferably about 20 to 8000 μm, andmore preferably about 30 to 5000 μm. Moreover, the fiber diameter is,for example, about 1 to 50 μm, preferably about 2 to 40 μm, and morepreferably 3 to 30 μm.

[0110] In the plate-like filler, the particle size is not less than 20μm and preferably about 25 to 500 μm, and the thickness is about 0.1 to10 μm and preferably about 0.3 to 5 μm.

[0111] In the particulate filler, the particle size is, for example, notmore than 100 μm (e.g., about 0.1 to 80 μm), preferably about 0.2 to 70μm, and more preferably about 0.3 to 60 μm.

[0112] Such inorganic fillers may be used singly or in combination. Thepreferred inorganic filler includes a glass fiber, and a glass flake.

[0113] The surface-treatment agent or sizing agent for treating theinorganic filler comprises a novolak epoxy resin. It seems that thesurface treatment of the inorganic filler with the novolak epoxy resinimproves flame retardancy (particularly inhibits dripping) probablybecause such a surface treatment facilitates carbonization (particularlysuch a surface treatment forms a carbonized firm coating on the surfaceof the inorganic filler) in compared with a treatment with othersurface-treatment agent or sizing agent (e.g., a bisphenol A-based epoxyresin).

[0114] Examples of the novolak resin constituting the novolak epoxyresin include a hovolak resin in which an alkyl group (e.g., aC₁₋₂₀alkyl group, preferably a C₁₋₄ alkyl group such as methyl group andethyl group) may be substituted on the aromatic ring (e.g., aphenol-novolak resin, a cresol-novolak resin). The preferred novolakepoxy resin includes a glycidyl ether of a novolak resin which may besubstituted with a C₁₋₂alkyl group. Incidentally, the novolak epoxyresin may be used in combination with a conventional sizing agent orsurface-treatment agent, e.g., a functional compound such as anepoxy-series compound (e.g., a bisphenol A-based epoxy resin, abisphenol A-based phenoxy resin), a urethane-series resin, an acrylicresin, a vinyl acetate-series resin, a fluorine-series resin, asilane-series compound and a titanate-series compound, a lubricant, anantistatic agent, and others.

[0115] The number average molecular weight of the novolak epoxy resinis, for example, about 200 to 50,000, preferably about 300 to 10,000,and more preferably about 400 to 6,000 (e.g., about 400 to 5,000).

[0116] The treatment of the inorganic filler is not particularly limitedto a specific one. For example, the inorganic filler may be pretreatedwith the surface-treatment agent or sizing agent, and added to the resincomposition, or may be treated by adding the surface-treatment agent orsizing agent to the kneading system with preparing the resincomposition.

[0117] In the surface treatment, the amount of the surface-treatmentagent or sizing agent is about 0.01 to 30 parts by weight, preferablyabout 0.05 to 20 parts by weight, and more preferably about 0.1 to 5parts by weight, relative to 100 parts by weight of the inorganicfiller.

[0118] The production process of the inorganic filler may be referred toJapanese Patent Application Laid-Open No. 248743/1988 (JP-63-248743A),Japanese Patent Application Laid-Open No. 48440/1990 (JP-2-48440A),Japanese Patent Application Laid-Open No. 79793/1999 (JP-11-79793A),Japanese Patent Application Laid-Open No. 172055/2001 (JP-2001-172055A),and others.

[0119] The proportion of the surface-treated inorganic filler (C) isabout 1 to 200 parts by weight, preferably about 3 to 180 parts byweight, and more preferably about 5 to 150 parts by weight, relative to100 parts by weight of the polyester-series resin (A).

[0120] [Additive]

[0121] If necessary, the flame-retardant resin composition of thepresent invention may comprise a variety of additives (for example, astyrenic resin (D), other flame-retardant auxiliary or synergist (orflame retardant) (E), an antioxidant (F), a stabilizer (G), a drippinginhibitor (H)). The total content of the additive(s) is about 0.01 to 50parts by weight, preferably about 0.1 to 40 parts by weight, and morepreferably about 0.5 to 35 parts by weight, relative to 100 parts byweight of the polyester-series resin.

[0122] (D) Styrenic Resin

[0123] The resin composition of the present invention may furthercomprise a styrenic resin.

[0124] As the styrenic resin, for example, there may be mentioned ahomo- or copolymer of a styrenic monomer (e.g., styrene, vinyltoluene,α-methylstyrene); a copolymer of the styrenic monomer and a vinylmonomer [e.g., an unsaturated nitrile (such as acrylonitrile), anα,β-monoolefinic unsaturated carboxylic acid or acid anhydride or anester thereof (such as a (meth)acrylic acid ester, (meth)acrylic acid,and maleic anhydride)]; a styrenic graft copolymer; a styrenic blockcopolymer; an epoxy-modified styrenic resin which is modified with aperoxide; and others.

[0125] The preferred styrenic resin includes a polystyrene [GPPS, SPS(syndiotactic polystyrene)], a styrene-methyl methacrylate copolymer, astyrene-(meth)acrylic acid copolymer, a styrene-glycidyl (meth)acrylatecopolymer, a styrene-maleic anhydride copolymer, a styrene-acrylonitrilecopolymer (AS resin), a styrene-acrylonitrile-glycidyl (meth)acrylatecopolymer, a high impact polystyrene (HIPS) in which a styrenic monomeris polymerized to a rubber component, and a polystyrenic graft or blockcopolymer. As the polystyrene-series graft copolymer, there maybementioned a copolymer in which at least a styrenic monomer and acopolymerizable monomer are grafted to a rubber component (for example,ABS resin which is obtained by graft polymerization of styrene andacrylonitrile to a polybutadiene, AAS resin which is obtained by graftpolymerization of styrene and acrylonitrile to an acrylic rubber, ACSresin which is obtained by graft polymerization of styrene andacrylonitrile to a chlorinated polyethylene, a polymer which is obtainedby graft polymerization of styrene and acrylonitrile to anethylene-vinyl acetate copolymer, a polymer which is obtained by graftpolymerization of styrene and acrylonitrile to an ethylene-propylenerubber, MBS resin which is obtained by graft polymerization of styreneand methyl methacrylate to a polybutadiene, a resin which is obtained bygraft polymerization of styrene and acrylonitrile to a styrene-butadienecopolymer rubber). The block copolymer includes a copolymer comprising apolystyrenic block and a diene or olefinic block (e.g., astyrene-butadiene-styrene (SBS) block copolymer, a styrene-isopreneblock copolymer, a styrene-isoprene-styrene (SIS) block copolymer, ahydrogenated styrene-butadiene-styrene (SEBS) block copolymer, ahydrogenated styrene-isoprene-styrene (SEPS) block copolymer), anepoxy-modified SBS, an epoxy-modified SIS, and others.

[0126] The number average molecular weight of the styrenic resin is notparticularly limited to a specific one, and may for example be selectedwithin the range of about 5×10³ to 200×10⁴, preferably about 1×10⁴ to150×10⁴, and more preferably about 1×10⁴ to 100×10⁴.

[0127] These styrenic resins may be used singly or in combination. Thecontent of the styrenic resin may for example be selected within therange of about 0 to 30 parts by weight, preferably about 0 to 20 partsby weight, and particularly about 0 to 15 parts by weight, relative to100 parts by weight of the polyester-series resin.

[0128] (E) Flame-Retardant Auxiliary

[0129] Examples of the flame-retardant auxiliary (or flame-retardantsynergist) include a resinous flame-retardant auxiliary (E1), aninorganic flame-retardant auxiliary (E2), or others. Theseflame-retardant auxiliaries may be used singly or in combination.

[0130] (E1) Resinous Flame-Retardant Auxiliary

[0131] The resinous flame-retardant auxiliary (or flame retardant)includes an aromatic-series resin (aromatic resin) such as (i) a resinof which the main chain or side chain contains an aromatic ring havingat least one group selected from a hydroxyl group and an amino group,(ii) a polyarylate-series resin, (iii) an aromatic epoxy resin, and (iv)a polycarbonate-series resin.

[0132] (i) Resin of which the Main Chain or Side Chain Contains anAromatic Ring having at least One Group Selected from a Hydroxyl Groupand an Amino Group

[0133] The resin of which the main chain contains the aromatic ringincludes (i-1) a novolak resin, (i-2) an aniline-aldehyde resin, (i-3)an aralkyl resin, and others. As the resin of which the side chaincontains the aromatic ring, there may be mentioned (i-4) an aromaticvinyl resin.

[0134] (i-1) Novolak Resin

[0135] The novolak resin includes a random phenol-novolak resin (e.g., amonomerless phenol-novolak resin, and a dimerless phenol-novolak resin;for example, such resins are procurable from Sumitomo Durez Co., Ltd. astrade name “SUMILITE RESIN PR-53647”, “SUMILITE RESIN PR-NMD-100series”, and “SUMILITE RESIN PR-NMD-200 series”), a high-orthonovolakresin [e.g., a high-orthonovolak resin having an ortho/para ratio of notless than 1 (e.g., about 1 to 20 (particularly about 1 to 15)); forexample, such a resin is procurable from Sumitomo Durez Co., Ltd. astrade name “SUMILITE RESIN HPN series”], a cresol-novolak resin, anaminotriazine-modified phenol-novolak resin, and others. The novolakresin is usually obtainable by a reaction of a phenol with an aldehyde(e.g., an aliphatic aldehyde such as formaldehyde and acetaldehyde; anaromatic aldehyde such as phenylacetaldehyde; a condensate offormaldehyde such as trioxane and paraformaldehyde). Examples of thephenol include a monohydric phenol such as phenol, p- or m-cresol,3,5-xylenol, an alkylphenol (e.g., a C₁₋₂₀alkylphenol such ast-butylphenol and octylphenol), and an arylphenol (e.g., phenylphenol,benzylphenol, and cumylphenol). The proportion (molar ratio) of thephenol relative to the aldehyde [the former/the latter] is about 2/1 to1/1.

[0136] The aminotriazine-modified novolak resin is a co-condansate ofthe phenol with a triazine as a co-condensable component (e.g., urea,cyanuric acid, isocyanuric acid, melamine, guanamine, acetoguanamine,and benzoguanamine), and is, for example, available from Dainippon InkAnd Chemicals, Inc. as trade name“PHENOLITE”. Moreover, the novolakresin also includes a resin obtained by using an aniline as aco-condensate component (e.g., aniline, o-toluidine, N-benzylaniline,and α- or β-naphthylamine).

[0137] The number average molecular weight of the novolak resin is notparticularly limited to a specific one, and is, for example, about 300to 5×10⁴, preferably about 300 to 1×10⁴, and more preferably about 300to 8000 (particularly, about 300 to 5000).

[0138] (i-2) Aniline-Aldehyde Resin

[0139] Examples of the aniline-aldehyde resin include a resin obtainableby a condensation of an aniline with an aldehyde. The aldehyde includesan aldehyde exemplified in the paragraph of the novolak resin (e.g.,formaldehyde), in addition furfural, benzaldehyde, or a mixture thereof,and others. Moreover, the aniline includes aniline, o-toluidine,N-benzylaniline, α- or β-naphthylamine, or a mixture thereof, andothers. Further, examples of the aniline-aldehyde resin also include aresin obtainable by using, as a co-condensable component, a phenol,urea, a triazine (a melamine or a derivative thereof, such as melamine,cyanuric acid and isocyanuric acid; a guanamine or a derivative thereof,such as guanamine, acetoguanamine and benzoguanamine).

[0140] The proportion (molar ratio) of the aniline relative to thealdehyde [the former/the latter] is about 2/1 to 1/1.

[0141] (i-3) Aralkyl Resin

[0142] The aralkyl resin includes a phenol-aralkyl resin obtainable by areaction of an aralkyl [an aralkyl ether such as a xylylene glycolC₁₋₄alkyl ether (e.g., p-xylylene glycol dimethyl ether, p-xylyleneglycol diethyl ether); an acyloxyaralkyl such asp-xylylene-α,α′-diacetate; an aralkyldiol such as p-xylylene-α,α′-diol;an aralkyl halide such as p-xylylene-α,α′-dichloride andp-xylylene-α,α′-dibromide] with a phenol (a phenol and an alkylphenolwhich are exemplified in the paragraph of the novolak resin); ananiline-aralkyl resin obtainable by a reaction of the aralkyl with theaniline [aniline, an alkylaniline (e.g., a C₁₋₂₀alkylaniline such astoluidine and xylidine), and by a reaction of the aralkyl with anN-alkylaniline (e.g., an N-C₁₋₄alkylaniline such asN,N-dimethylaniline)]; and others. Moreover, as other aralkyl resin,there may be used an aralkyl resin described in Japanese PatentApplication Laid-Open No. 351822/2000 (JP-2000-351822A). If necessary,the aralkyl resin may be cured or epoxy-modified.

[0143] The proportion of the aralkyl relative to the phenol or aniline[the former/the latter] is, for example, about 1/1 to 1/3 (molar ratio),and preferably about 1/1 to 1/2.5 (molar ratio).

[0144] (i-4) Aromatic Vinyl Resin

[0145] The aromatic vinyl resin includes a homo- or copolymer of anaromatic vinyl monomer. As the aromatic vinyl monomer, for example,there may be mentioned a hydroxyl group-containing aromatic vinylmonomer such as vinylphenol, dihydroxystyrene and vinylnaphthol. Thesearomatic vinyl monomers may be used singly or in combination.

[0146] Examples of the other copolymerizable monomer are a (meth)acrylicmonomer [e.g., (meth)acrylic acid, a (meth)acrylate (e.g., a C₁₋₁₈alkyl(meth)acrylate such as methyl (meth)acrylate; (meth)acrylamide; and(meth)acrylonitrile], a styrenic monomer (e.g., styrene, vinyltoluene,and a-methylstyrene), a polymerizable polycarboxylic acid (e.g., fumaricacid, and maleic acid), a maleimide-series monomer (e.g., maleimide, andan N-alkylmaleimide), a diene-series monomer (e.g., isoprene, and1,3-butadiene), and a vinyl-series monomer (e.g., a vinyl ester such asvinyl acetate; a vinyl ketone such as methyl vinyl ketone; and a vinylether such as vinyl isobutyl ether). These copolymerizable monomers maybe used either singly or in combination.

[0147] The ratio of the vinyl monomer relative to the copolymerizablemonomer is, for example, about 10/90 to 100/0 (% by weight), preferablyabout 30/70 to 100/0 (% by weight), and more preferably about 50/50 to100/0 (% by weight).

[0148] The preferred aromatic vinyl resin includes a polyvinylphenolresin [e.g., a vinylphenol homopolymer (a polyhydroxystyrene),particularly a p-vinylphenol homopolymer], a vinylphenol-styrenecopolymer, and others.

[0149] There is no particular restriction as to the number averagemolecular weight of the aromatic vinyl-series resin, and it may beselected within the range of, for example, 300 to 50×10⁴, preferably 400to 30×10⁴, and more preferably about 500 to 5×10⁴.

[0150] (ii) Polyarylate-Series Resin

[0151] As the polyarylate-series resin, there may be used apolyarylate-series resin obtained through a polyesterification reactionof an aromatic polyol component with a polycarboxylic acid component(e.g., an aromatic polycarboxylic acid component, an aliphaticpolycarboxylic acid component, and an alicyclic polycarboxylic acidcomponent). It is preferred that the polycarboxylic acid componentusually contains at least an aromatic polycarboxylic acid component.

[0152] The polyarylate-series resin includes a polyarylate-series resinin which an aromatic polyol component is a benzenediol and/or abisphenol and a polycarboxylic acid component is an aromaticpolycarboxylic acid, and for example includes a polyester obtained froma benzenediol (e.g., hydroquinone, resorcinol, m-xylylene glycol, andp-xylylene glycol) and/or a bisphenol (e.g., bisphenol A, bisphenol AD,bisphenol F, and biphenol) and a benzenedicarboxylic acid (e.g.,isophthalic acid, and terephthalic acid), and a polyester obtained froma bisphenol and a bis(arylcarboxylic acid) [e.g., a bis(carboxyaryl)C₁₋₄alkyl such as a bis(carboxyphenyl)methane, a bis(carboxyphenyl)ethaneand a bis(carboxyphenyl)propane]. These polyarylate-series resins may beused singly or in combination.

[0153] Moreover, the polyarylate-series resin may be a resin using, ifnecessary an aromatic triol, an aromatic tetraol [e.g.,1,1,2,2-tetrakis(hydroxyphenyl)ethane], an aromatic tricarboxylic acid,or an aromatic tetracarboxylic acid, in addition to an aromatic diol andan aromatic dicarboxylic acid.

[0154] The terminal (or end) of the polyarylate-series resin may beblocked with (bonded to) an alcohol [e.g., a monohydric phenol which mayhave a C₁₋₁₀alkyl group and/or a C₆₋₁₀aryl group as a substituent (e.g.,phenol, and a C₁₋₄alkyl-phenol), a C₁₋₂₀alkylmonoalcohol (e.g.,methanol, and ethanol), a C₇₋₂₀aralkyl monoalcohol (e.g., benzylalcohol)], or a carboxylic acid [e.g., a C₁₋₂₀aliphatic monocarboxylicacid (e.g., acetic acid, and propionic acid), a C₄₋₂₀alicyclicmonocarboxylic acid (e.g., ccyclohexanecarboxylic acid), a C₇₋₂₀aromaticmonocarboxylic acid (e.g., benzoic acid), a C₁₋₁₀aliphaticmonocarboxylic acid having a C₆₋₂₀aromatic group as a substituent (e.g.,phenylacetic acid)].

[0155] Moreover, the polyarylate-series resin may constitute a polymeralloy with other resin (e.g., a polyester, a polyamide, and apolycarbonate). The polymer alloy includes not only a simple mixture butalso a transesterified polymer alloy or a polymer alloy containing acompatibilizing agent.

[0156] The number average molecular weight of the polyarylate-seriesresin is, for example, about 300 to 30×10⁴, preferably about 500 to10×10⁴, and more preferably about 500 to 5×10⁴.

[0157] (iii) Aromatic Epoxy Resin

[0158] Examples of the aromatic epoxy resin include an ether-seriesepoxy resin (e.g., a bisphenol-based epoxy resin) and an amine-seriesepoxy resin formed with an aromatic amine component.

[0159] Examples of the bisphenol constituting a bisphenol-based epoxyresin are the same as the bis(hydroxyaryl) listed above. The preferredbisphenol-based epoxy resin includes a glycidyl ether of abis(hydroxyaryl)C₁₋₆alkane, particularly bisphenol A, bisphenol AD,bisphenol F or the like. Moreover, examples of the bisphenol-based epoxyresin also include the above-mentioned bisphenol glycidyl ether of highmolecular weight (that is, a phenoxy resin).

[0160] Examples of the aromatic amine component constituting theamine-series epoxy resin are a monocyclic aromatic amine (e.g., aniline,toluidine), a monocyclic aromatic diamine (e.g., diaminobenzene,xylylenediamine), a monocyclic aromatic aminoalcohol (e.g.,aminohydroxybenzene), a polycyclic aromatic diamine (e.g.,diaminodiphenylmethane), and a polycyclic aromatic amine.

[0161] The number average molecular weight of the epoxy resin is, forexample, about 200 to 50,000, preferably about 300 to 10,000, and morepreferably about 400 to 6,000 (e.g., about 400 to 5,000). Moreover, thenumber average molecular weight of the phenoxy resin is, for example,about 500 to 50,000, preferably 1,000 to 40,000, and more preferablyabout 3,000 to 35,000.

[0162] The epoxy resin may be used in a cured state, and the curing iseffected by the use of a curing agent, e.g., an amine-series curingagent (e.g., an aliphatic amine such as ethylenediamine; an aromaticamine such as metaphenylenediamine and xylylenediamine), apolyaminoamide-series curing agent, an acid and acid anhydride-seriescuring agent.

[0163] These resin components may be used singly or in combination.

[0164] (iv) Polycarbonate-Series Resin

[0165] The polycarbonate-series resin includes a polymer obtainablethrough the reaction of a dihydroxy compound with phosgene or a carbonicester such as diphenyl carbonate. Examples of the dihydroxy compoundinclude an alicyclic compound (e.g., an alicyclic diol exemplified inthe paragraph of the polyester-series resin), a bisphenol compound, andothers. Incidentally, at least one member of the dihydroxy compound andthe carbonic ester is an aromatic compound.

[0166] The bisphenol compound includes a bisphenol exemplified in theparagraph of the novolak resin (in particular abis(hydroxyaryl)C₁₋₆alkane, a bis(hydroxyaryl)C₄₋₁₀cycloalkane,4,4′-dihydroxydiphenyl ether; 4,4′-dihydroxydiphenyl sulfone;4,4′-dihydroxydiphenyl sulfide; 4,4′-dihydroxydiphenyl ketone; andothers).

[0167] The content of the resinous flame-retardant auxiliary may forexample be selected within the range of about 1 to 30 parts by weight,preferably about 3 to 25 parts by weight, and more preferably about 5 to20 parts by weight relative to 100 parts by weight of thepolyester-series resin.

[0168] These resinous flame-retardant auxiliaries may be used singly orin combination.

[0169] (E2) Inorganic Flame-Retardant Auxiliary

[0170] As the inorganic flame-retardant auxiliary (or flame retardant)(E2), there may be mentioned a metal salt of an inorganic acid (i), ametal oxide (ii), a metal hydroxide (iii), a metal sulfide (iv), a redphosphorus (v), and others.

[0171] (i) Metal Salt of Inorganic Acid

[0172] As the inorganic acid constituting the salt, there may be used anoxygen acid [for example, an oxygen acid, e.g., nitric acid, a chloricacid (such as perchloric acid chloric acid, chlorous acid andhypochlorous acid), a phosphoric acid, a sulfuric acid, a boric acid, achromic acid, an antimonic acid], a halogen acid (e.g., a hydrochloricacid), a carbonic acid, and others. Incidentally, the phosphoric acid,the sulfuric acid and the boric acid may be non-condensed or condensed,and there may be used a phosphoric acid, a sulfuric acid and a boricacid, each exemplified in the paragraph of the salt of the oxygen acidin the nitrogen-containing cyclic compound (B3).

[0173] A metal forming a salt with the inorganic acid includes an alkalimetal (e.g., potassium, sodium); an alkaline earth metal (e.g.,magnesium, calcium, barium); a transition metal [e.g., the metal of theGroup 3A of the Periodic Table of Elements (such as scandium); the metalof the Group 4A of the Periodic Table of Elements (such as titanium);the metal of the Group 5A of the Periodic Table of Elements (such asvanadium); the metal of the Group 6A of the Periodic Table of Elements(such as chromium, molybdenum and tungsten); the metal of the Group 7Aof the Periodic Table of Elements (such as manganese); the metal of theGroup 8 of the Periodic Table of Elements (such as iron, cobalt, nickeland palladium); and the metal of the Group 1B of the Periodic Table ofElements (such as copper and silver)], the metal of the Group 2B of thePeriodic Table of Elements (such as zinc, cadmium and mercury), themetal of the Group 3B of the Periodic Table of Elements (such asaluminum), the metal of the Group 4B of the Periodic Table of Elements(such as tin and lead), and the metal of the Group 5B of the PeriodicTable of Elements (such as antimony and bismuth). These metals may beused singly or in combination.

[0174] (i-1) Metal Phosphate

[0175] The phosphoric acid includes a non-condensed phosphoric acid, acondensed phosphoric acid (a polyphosphoric acid), and others. Inparticular, a non-condensed phosphoric acid is preferred.

[0176] The metal preferably includes a polyvalent metal, for example,the alkaline earth metal, the transition metal and the metals of theGroups 2B and 3B of the Periodic Table of Elements, particularly thealkaline earth metal.

[0177] As the metal phosphate (or metal salt of a phosphoric acid),there may be mentioned a salt of the phosphoric acid with the polyvalentmetal, in addition a hydrogenphosphate corresponding to the polyvalentmetal phosphate. The metal salt may have a ligand (e.g., hydroxo,halogen).

[0178] As the metal phosphate, there may be used, for example, apyrophosphate (such as Ca₂P₂O₇), a polymetaphosphate (such asCa₃(P₃O₉)₂), a salt of anhydrous phosphoric acid (such as Ca₂(P₄O₁₂) andCa₅(P₃O₁₀)₂), in addition a condensed phosphate (such as Ca₅(PO₄)₃(OH)and Ca₅(PO₄)₃(F, Cl)), and there is preferably used a hydrogenphosphate.

[0179] Such a hydrogenphosphate includes, for example, a non-condensedhydrogenphosphate such as an alkaline earth metal hydrogenphosphate[e.g., a magnesium hydrogenorthophosphate (such as magnesiumhydrogenphosphate and magnesium dihydrogenphosphate), a calciumhydrogenorthophosphate (such as calcium dihydrogenphosphate and calciumsecondary phosphate) 1; a transition metal hydrogenphosphate [e.g.,manganese hydrogenphosphate (such as manganese (III) hydrogenphosphate),iron hydrogenphosphate (such as Fe(H₂PO₄₎ ₃)]; a hydrogenphosphate ofthe metal of the Group 2B of the Periodic Table of Elements (such aszinc hydrogenphosphate and cadmium hydrogenphosphate); ahydrogenphosphate of the metal of the Group 3B of the Periodic Table ofElements (such as aluminum hydrogenphosphate); and a hydrogenphosphateof the metal of the Group 4B of the Periodic Table of Elements (such astin hydrogenphosphate). Among them, a substantially anhydrous metalhydrogenphosphate, particularly an alkaline earth metalhydrogenphosphate [such as magnesium dihydrogenphosphate, calciumdihydrogenphosphate and calcium secondary phosphate (CaHPO₄)], ispreferred.

[0180] (i-2) Metal Borate

[0181] The boric acid preferably includes a non-condensed boric acidsuch as orthoboric acid and metaboric acid; a condensed boric acid suchas pyroboric acid, tetraboric acid, pentaboric acid and octaboric acid;and a basic boric acid.

[0182] As the metal, the alkali metal may be used, and it is preferredto use a polyvalent metal such as the alkaline earth metal, thetransition metal and the metal of the Group 2B of the Periodic Table ofElements.

[0183] The metal borate is usually a salt hydrate and includes, forexample, a non-condensed borate [e.g., a non-condensed borate of analkaline earth metal (such as calcium orthoborate and calciummetaborate); a non-condensed borate of a transition metal (such asmanganese orthoborate and copper metaborate); a non-condensed borate ofthe metal of the Group 2B of the Periodic Table of Elements (such aszinc metaborate and cadmium metaborate), in particular metaborate], acondensed borate [e.g., a condensed borate of an alkaline earth metal(such as trimagunesium tetraborate and calcium pyroborate); a condensedsalt of a transition metal (such as manganese tetraborate and nickeldiborate); a condensed borate of the metal of the Group 2B of thePeriodic Table of Elements (such as zinc tetraborate and cadmiumtetraborate)], and a basic borate (e.g., a basic borate of the metal ofthe Group 2B of the Periodic Table of Elements, such as basic zincborate and basic cadmium borate). Moreover, a hydrogenboratecorresponding to the borate (e.g., manganese hydrogenorthoborate) may bealso employed. In particular, a borate of the alkaline earth metal ormetal of the Group 2B of the Periodic Table of Elements (a non-condensedor condensed borate) (particularly a (hydrous) calcium borate, a(hydrous) zinc borate) is preferred.

[0184] As a metal salt of an inorganic acid (oxygen acid: e.g., astannic acid, a molybdic acid, and a tungstic acid) other than aphosphoric acid and a boric acid, there may be used various metal saltscorresponding to the metal phosphate and metal borate.

[0185] (ii) Metal Oxide

[0186] The metal oxide includes, for example, molybdenum oxide, tungsticoxide, titanium oxide, zirconium oxide, tinoxide, copperoxide,zincoxide, aluminumoxide, nickel oxide, iron oxide, manganese oxide,antimony trioxide, antimony tetraoxide, antimony pentaoxide, and others.

[0187] (iii) Metal Hydroxide

[0188] The metal hydroxide includes, for example, aluminum hydroxide,magnesium hydroxide, tin hydroxide, zirconium hydroxide, nickelhydroxide, and magnesium hydroxide modified with nickel hydroxide.

[0189] (iv) Metal Sulfide

[0190] As the metal sulfide, there may be mentioned zinc sulfide,molybdenum sulfide, tungstic sulfide, and others.

[0191] (v) Red Phosphorus

[0192] As the red phosphorus, usually, a red phosphorus which hasundergone stabilization treatment (that is, a stabilized red phosphorus)is preferably employed. Particularly preferred are a red phosphoruswhich is obtained by finely dividing without pulverization and formationof the pulverized surface highly reactive to water or oxygen, and a redphosphorus the surface of which is coated with one member or acombination of two or more members selected from resins (e.g.,thermosetting resins, thermoplastic resins), metals, metal compounds(e.g., metal hydroxides, metal oxides).

[0193] Exemplified as the thermosetting resin are a phenolic resin, amelamine-series resin, a urea-based resin, an alkyd resin, anunsaturated polyester-series resin, an epoxy resin, and asilicone-series resin, and examples of the thermoplastic resin are apolyester-series resin, a polyamide-series resin, an acrylic resin, anolefinic resin, and others. Examples of the metal hydroxide are aluminumhydroxide, magnesium hydroxide, calcium hydroxide, zinc hydroxide, andtitanium hydroxide. Examples of the metal oxide are aluminum oxide,magnesium oxide, zinc oxide, titanium oxide, zirconium oxide, copperoxide, iron oxide, molybdenum oxide, tungsten oxide, manganese oxide,and tin oxide.

[0194] Further, a process for coating with a metal the surface of thered phosphorus for stabilization includes a coating process with a metal(e.g., iron, nickel, copper, aluminum, zinc, manganese, tin, titanium,zirconium) or an alloy thereof through electroless plating. Otherprocesses for coating the surface of a red phosphorus include a processin which red phosphorus is treated with a solution of a metal salt(e.g., a salt with aluminum, magnesium, zinc, titanium, copper, silver,iron, nickel) to form a metal phosphorus compound on the red phosphorussurface for stabilization of the red phosphorus.

[0195] In particular, with the use of a process comprising pulverizingthe red phosphorus without forming a crushed surface thereon, the redphosphorus may be preferably subjected to coating treatment with aplurality of layers being a combination of a layer(s) of a metalcomponent(s) (e.g., metal hydroxide, metal oxide) and a resin layer(s),particularly with a metal component layer covered by a plurality ofresin layers. Such stabilized red phosphorus is excellent in heatstability and hydrolysis resistance and the amount of a phosphineproduced upon decomposition in the presence of moisture or under hightemperatures is so extremely small that they are preferable from theviewpoint of safety in the course of producing the resin composition ofthe present invention and a shaped article molded therefrom.

[0196] Such stabilized red phosphorus can be prepared referring toJapanese Patent Application Laid-Open No. 229806/1993 (JP-5-229806A),Japanese Patent Application Laid-Open No. 259956/1991 (JP-3-259956A),Japanese Patent Application Laid-Open No. 209991/1990 (JP-2-209991A),Japanese Patent Application Laid-Open No. 150309/1989 (JP-1-150309A),Japanese Patent Application Laid-Open No. 21704/1987 (JP-62-21704A),Japanese Patent Application Laid-Open No. 125489/1977 (JP-52-125489A),EP 296501A1, and EP249723A2.

[0197] As the red phosphorus, a stabilized one in the form of particlesmay be usually employed. The mean particle size of the stabilized redphosphorus is, for example, about 0.01 to 100 μm, preferably about 0.1to 70 μm, and more preferably about 0.1 to 50 μm.

[0198] These inorganic flame-retardant auxiliaries may be used singly orin combination. The content of the inorganic flame-retardant auxiliary(in particular a metal salt of an inorganic acid) may for example beselected within the range of about 0.5 to 30 parts by weight, preferablyabout 2 to 20 parts by weight, and more preferably about 3 to 15 partsby weight, relative to 100 parts by weight of the polyester-seriesresin.

[0199] Incidentally, the flame-retardant resin composition of thepresent invention may comprise, in order to further impart flameretardancy to the composition, a second flame retardant(s) (E3), forexample, a nitrogen-containing flame retardant (E3a), asulfur-containing flame retardant (E3b), a silicon-containing flameretardant (E3c), an alcohol-based flame retardant (E3d), an expansivegraphite (E3e), and others. (E3a) Nitrogen-containing flame retardantThe nitrogen-containing flame retardant includes a urea compound (anon-cyclic urea compound, a cyclic urea compound), and guanidinecompound.

[0200] Examples of the non-cyclic urea compound include urea, anN-substituted urea having a substituent such as an alkyl group, anon-cyclic urea condensate [for example, a polymer of urea (e.g., adimer such as biuret, biurea, and IB nitrogen), a condensate of ureawith an aldehyde compound (e.g., methylene diurea, ureaform, and a urearesin)], and others. Incidentally, the urea resin also includes a resinobtained by using, as a co-condensable component, a phenol, a triazine(e.g., a melamine or a derivative thereof such as melamine, cyanuricacid, and isocyanuric acid; a guanamine or a derivative thereof such asguanamine, acetoguanamine, and benzoguanamine), an aniline (e.g.,aniline, o-toluidine, N-benzylaniline, α- or β-naphthylamine), andothers.

[0201] The cyclic compound having a urea unit (or cyclic urea compound)is not particularly limited to a specific one as far as the compoundcomprises at least one urea unit (—NHCONH—) as a constituent unit of aring thereof, and may be any of a monocyclic compound, and a condensedring with an aromatic hydrocarbon ring or crosslinked ring. The cyclicurea compound includes a cyclic monoureide, a cyclic diureide, andothers. Further, the cyclic urea compound also includes a cyclicthiourea compound corresponding to the above-mentioned cyclic ureacompound. These cyclic urea compounds may be used singly or incombination.

[0202] As the cyclic monoureide, for example, there may be mentioned analkyleneurea [e.g., a C₁₋₁₀alkyleneurea such as methyleneurea,ethyleneurea and crotonylideneurea (CDU) (preferably, aC₁₋₆alkyleneurea)], an alkenyleneurea (e.g., a C₂₋₁₀alkenyleneurea suchas vinyleneurea and cytosine), an alkynyleneurea [e.g., aC₂₋₁₀alkynyleneurea (preferably, a C₂₋₆alkynyleneurea)], an aryleneurea(e.g., imesatin), a ureide of a dicarboxylic acid (e.g., parabanic acid,dimethylparabanic acid, barbituric acid, 5,5-diethylbarbituric acid,dilituric acid, dialuric acid, alloxan, alloxanic acid, isocyanuricacid, uramil), a ureide of a β-aldehydic acid (e.g., uracil,5-methyluracil (thymine), dihydrouracil, urazole, benzolyene urea), aureide of a α-hydroxy acid [e.g., a hydantoin compound such ashydantoin, 5,5-dimethylhydantoin,1,1-methylenebis(5,5-dimethylhydantoin) and allantoin], or a derivativethereof.

[0203] As the cyclic diureide, for example, there may be mentioned uricacid, an alkyl-substituted uric acid (e.g., a C₁₋₄alkyluric acid such as3-methyluric acid), pseudouric acid, acetyleneurea (glycoluril), adiureide of an α-hydroxy acid [e.g.,1,1-methylenebis(5,5-dimethylhydantoin), allantoin], a diurea such asp-urazine, a diureide of a dicarboxylic acid (e.g., alloxantin, purpuricacid), or a derivative thereof.

[0204] Further, among the compounds exemplified in the paragraph of thenitrogen-containing cyclic compound having a hydroxyl group, there maybe used a compound having an enol form of a urea as a constituent unit[that is, a compound whose tautomer has a urea unit (such as ammelineand ammelide)], and others.

[0205] Among the cyclic urea compounds, the preferred compound includesa cyclic diureide having two urea units as a constituent unit of a ringthereof (including a cyclic thiourea having two urea units), inparticular acetyleneurea, uric acid, and a derivative thereof.

[0206] The cyclic urea compound (particularly, the derivative of theacetyleneurea or uric acid) also includes a salt thereof. As the salt,there is not particularly limited to a specific one as far as forming asalt with the cyclic urea compound, and there may be mentioned a salt ofthe cyclic urea compound with at least one member selected from atriazine compound, an oxygen acid and an organic phosphoric acid, eachexemplified in the paragraph of the nitrogen-containing cyclic compound,and metals exemplified in the paragraph of the above-mentioned (E2). Inparticular, a salt of the cyclic urea compound with the triazinecompound and/or the metal is preferred. These salts may be used singlyor in combination.

[0207] Among the above-mentioned triazine compounds, melamine, amelamine condensate (e.g., melem, melam, melon), and guanamine areparticularly preferred as a triazine compound forming a salt.

[0208] As a metal forming a salt, there may be mentioned an alkali metal(e.g., sodium, potassium, and lithium), an alkaline earth metal (e.g.,calcium, magnesium, and barium), and a transition metal (e.g., iron,copper, cobalt, and manganese).

[0209] The proportion of the cyclic urea compound relative to thesalifiable component is not particularly limited to a specific one, andfor example the former/the latter (molar ratio) is about 1/5 to 4/1,preferably about 1/3 to 2/1, and more preferably about 1/2 to 1/1.

[0210] The guanidine compound includes a non-cyclic guanidine compoundand a cyclic guanidine compound. Examples of the non-cyclic guanidinecompound include cyanoguanidine (dicyandiamide), glycocyamine, guanolin,creatine or a derivative thereof, and others. The cyclic guanidinecompound includes a glycocyamidine (e.g., glycocyamidine,thioglycocyamidine, creatinine, 4-methylglycocyamidine), anoxalylguanidine (e.g., oxalylguanidine, 2,4-diiminoparabanic acid), animinourazole (e.g., iminourazole, guanazine), malonylguanidine,tartronoylguanidine, mesoxalylguanidine, and others.

[0211] (E3b) Sulfur-Containing Flame Retardant

[0212] Examples of the sulfur-containing flame retardant include asulfuric ester, in addition an organic sulfonic acid, sulfamic acid andan organic sulfamic acid, and a salt with these acids (e.g., an alkalimetal salt, and an alkaline earth metal salt), an ester with these acidsand an amide with these acids.

[0213] (E3c) Silicon-Containing Flame Retardant

[0214] The silicon-containing flame retardant includes a(poly)organosiloxane. As the (poly)organosiloxane, there may bementioned a homopolymer such as a dialkylsiloxane (e.g.,dimethylsiloxane), an alkylarylsiloxane (e.g., phenylmethylsiloxane), adiarylsiloxane, and a monoorganosiloxane (for instance, apolydimethylsiloxane, a polyphenylmethylsiloxane); or a copolymer; andothers. Moreover, the (poly)organosiloxane also includes a branchedorganosiloxane [e.g., trade name “XC99-B5664” manufactured by ToshibaSilicone Co., Ltd., trade name “X-40-9243”, “X-40-9244” and “X-40-9805”manufactured by Shin-Etsu Chemical Co., Ltd., and compounds described inJapanese Patent Application Laid-Open No. 139964/1998 (JP-10-139964A)],and a modified (poly)organosiloxane (for example, a modified silicone)having substituent(s) (such as an epoxy group, a hydroxyl group, acarboxyl group, an amino group, and an ether group) in the end or mainchain of the molecule.

[0215] (E3d) Alcohol-Based Flame Retardant

[0216] Examples of the alcohol-based flame retardant include apolyhydric alcohol, an oligomeric polyhydric alcohol, an esterifiedpolyhydric alcohol, a substituted alcohol, and a saccharide compound(e.g., a monosaccharide, a polysaccharide).

[0217] These second flame retardants (E3) may be used singly or incombination.

[0218] The content of the second flame retardant (E3) may for example beselected within the range of about 0 to 50 parts by weight (e.g., about0.01 to 50 parts by weight), preferably about 0.05 to 30 parts byweight, and particularly about 0.1 to 20 parts by weight, relative to100 parts by weight of the polyester-series resin.

[0219] Moreover, the flame-retardant resin composition of the presentinvention may comprise an antioxidant (F) or a stabilizer (G) tomaintain thermal stability of the composition for a long term.

[0220] The antioxidant or the stabilizer includes a phenol-series (e.g.,hindered phenols), a phosphorus-series, an amine-series (e.g., hinderedamines), a sulfur-series, a hydroquinone-series, or a quinoline-seriesantioxidant (or stabilizer), an inorganic stabilizer, a compound havinga functional group reactive to an active hydrogen atom (reactivestabilizer), and others.

[0221] (F1) Phenol-Series Antioxidant (Phenol-Series Stabilizer)

[0222] The phenol-series (phenolic) antioxidant preferably includes ahindered phenol (hindered phenol-series antioxidant), e.g., aC₂₋₁₀alkylene glycol-bis [3-(3,5-di-branched C₃₋₆alkyl-4-hydroxyphenyl)propionate] such as1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate]; e.g.,a di- or trioxyC₂₋₄alkylene glycol-bis[3-(3,5-di-branched C₃₋₆alkyl-4-hydroxyphenyl) propionate] such as triethyleneglycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate]; e.g., aC₃₋₈alkylenetriol-bis[3-(3,5-di-branched C₃₋₆alkyl-4-hydroxyphenyl)propionate] such as glycerin-tris[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]; and e.g., a C₄₋₈alkylenetetraol-tetrakis[3-(3,5-di-branched C₃₋₆alkyl-4-hydroxyphenyl)propionate] such aspentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate].

[0223] (F2) Phosphorus-Series (Phosphorus-Containing) Stabilizer orAntioxidant

[0224] The phosphorus-containing stabilizer (or antioxidant) includes anorganic phosphorus-containing stabilizer, for example, triisodecylphosphite, trisnonylphenyl phosphite, diphenylisodecyl phosphite,phenyldiisodecyl phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite, 4,4′-butylidenebis(3-methyl-6-t-butylphenyl)ditridecylphosphite, a bis- or tris(branched C₃₋₆alkylphenyl) phosphite [e.g.,bis- or tris(2-t-butylphenyl)phenyl phosphite,tris(2,4-di-t-butylphenyl)phosphite, tris(2-t-butyl-4-methylphenyl)phosphite, tris(2,4-di-t-amylphenyl) phosphite],tris(2-cyclohexylphenyl) phosphite, a bis(C₁₋₉alkylaryl)pentaerythritoldiphosphite [e.g., bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite,bis(2,4-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite,bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite,bis(nonylphenyl)pentaerythritol diphosphite], a triphenylphosphate-series stabilizer (e.g.,4-phenoxy-9-a-(4-hydroxyphenyl)-p-cumenyloxy-3,5,8,10-tetraoxa-4,9-diphosphaspiro[5.5]undecane,tris(2,4-di-t-butylphenyl) phosphate), and a diphosphonite-seriesstabilizer (e.g., tetrakis(2,4-di-t-butyl)-4,4′-biphenylenediphosphonite). The phosphorus-containing stabilizer usually has abranched C₃₋₆alkylphenyl group (particularly, t-butylphenyl group).

[0225] (F3) Amine-Series Antioxidant

[0226] The amine-series antioxidant includes a hindered amine, forexample, a tri- or tetraC₁₋₃alkylpiperidine or a derivative thereof[e.g., 2,2,6,6-tetramethylpiperidine which may have a substituent (suchas methoxy, benzoyloxy or phenoxy group) at 4-position], a bis (tri-,tetra- or pentaC₁₋₃alkylpiperidine) C₂₋₂₀alkylenedicarboxylic ester[e.g., bis(2,2,6,6-tetramethyl-4-piperidyl) oxalate, a melonate,adipate, sebacate and terephthalate corresponding to the oxalate; andbis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate],1,2-bis(2,2,6,6-tetramethyl-4-piperidyloxy)ethane, phenylnaphthylamine,N,N′-diphenyl-1,4-phenylenediamine, andN-phenyl-N′-cyclohexyl-1,4-phenylenediamine.

[0227] (F4) Hydroquinone-Series Antioxidant

[0228] The hydroquinone-series antioxidant includes, for example,2,5-di-t-butylhydroquinone, and the quinoline-series antioxidantincludes, for example, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinone. Thesulfur-series antioxidant includes, for example,dilaurylthiodipropionate, distearylthiodiproionate, and others.

[0229] (G1) Inorganic Stabilizer

[0230] The inorganic stabilizer includes an inorganic metal-seriesstabilizer (or a mineral stabilizer) such as a hydrotalcite and azeolite. As the hydrotalcite, hydrotalcites recited in Japanese PatentApplication Laid-Open No. 1241/1985 (JP-60-1241A) and Japanese PatentApplication Laid-Open No. 59475/1997 (JP-9-59475A), such as hydrotalcitecompounds represented by the following formula are usable.

[0231] [M²⁺ _(1-x)M³⁺ _(x)(OH)₂]^(x+)[A^(n−) _(x/n)·mH₂O]^(x−)

[0232] In the formula, M²⁺ represents Mg²⁺, Mn²⁺, Fe²⁺, Co²⁺, or any ofother divalent metal ions; M³⁺ represents Al³⁺, Fe³⁺, Cr³⁺, or any ofother trivalent metal ions; A^(n+) represents CO₃ ²⁻, OH⁻, HPO₄ ²⁻, SO₄²⁻, or any of other n-valent anions (particularly, monovalent ordivalent anion); x is 0<x<0.5; and m is 0≦m<1.

[0233] Incidentally, the hydrotalcite is available from Kyowa ChemicalIndustry Co., Ltd. under the trade name “DHT-4A”, “DHT-4A-2”, or“Alcamizer”.

[0234] The zeolite is not particularly limited to a specific one, andfor example, zeolites recited in Japanese Patent Application Laid-OpenNo. 62142/1995 (JP-7-62142A) [zeolites the smallest unit cell of whichis a crystalline aluminosilicate with an alkali and/or alkaline earthmetal (A-, X-, Y-, L-, and ZSM-type zeolites, mordenite-type zeolite;chabazite, mordenite, faujasite, and other naturally-occurringzeolites)] may be employed.

[0235] Incidentally, A-type zeolite is available as “ZEOLAM-series (A-3,A-4, A-5)”, “ZEOSTAR-series (KA100P, NA-100P, CA-100P)” or others,X-type zeolite as “ZEOLAM-series (F-9)”, “ZEOSTAR-series (NX-100P)” orothers, and Y-type zeolite as “HSZ-series (320NAA)” or others, fromTosoh Corp. or Nippon Chemical Industrial Co., Ltd. These inorganicstabilizers may be used singly or in combination.

[0236] (G2) Reactive Stabilizer

[0237] The reactive stabilizer includes a compound having a functionalgroup reactive to an active hydrogen atom.

[0238] Examples of the compound having a functional group reactive to anactive hydrogen atom include a compound having at least one functionalgroup selected from the group consisting of a cyclic ether group [e.g.,an oxetane group (or ring), an epoxy group], an acid anhydride group, anisocyanate group, an oxazoline group (or ring), an oxazine group (orring), and a carbodiimide group.

[0239] The compound having an epoxy group includes, for example, analicyclic compound such as vinylcyclohexene dioxide; a glycidyl estercompound such as glycidyl versatate; a glycidyl ether compound such as ahydroquinone diglycidyl ether, a biphenol diglycidyl ether, a bisphenolA diglycidyl ether (bisphenol A-based epoxy resin); a glycidylaminecompound; an epoxy group-containing vinyl copolymer; an epoxidizedpolybutadiene; an epoxidized diene-series monomer-styrene copolymer; atriglycidyl isocyanurate; an epoxy-modified (poly)organosiloxane; andothers.

[0240] Examples of the compound having an oxetane group include anoxetanyl ester compound such as di[1-ethyl(3-oxetanyl)]methylisophthalate and di[1-ethyl(3-oxetanyl) ]methyl terephthalate, anoxetanyl ether compound {for example, an alkyloxetanyl compound such asdi[1-ethyl(3-oxetanyl)]methyl ether and3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, an aryloxetanyl compound suchas 3-ethyl-3-(phenoxymethyl)oxetane, an aralkyloxetanyl ether compoundsuch as 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, abisphenol-based oxetane resin such as bisphenol-Adi[1-ethyl(3-oxetanyl)]methyl ether, a novolak oxetane resin such as amono- to poly[1-ethyl(3-oxetanyl)]methyl-etherized phenol novolak and amono- to poly[1-ethyl(3-oxetanyl)]methyl-etherized cresol novolak), anoxetane-modified (poly)organosiloxane such as3-ethyl-3-([3-(triethoxysilyl)propoxy]methyl}oxetane, and a derivativehaving an alkyloxetanyl unit (e.g., a derivative having analkyl(3-oxetanyl)methyl unit) corresponding to the derivative having theoxetanyl unit (e.g., the derivative having the[1-ethyl(3-oxetanyl)]methyl unit), and others.

[0241] The compound having an acid anhydride group includes, forexample, an olefinic resin having a maleic anhydride group (e.g., anethylene-maleic anhydride copolymer, a maleic anhydride-modifiedpolypropylene), and others.

[0242] Examples of the compound having an isocyanate group include analiphatic isocyanate such as hexamethylene diisocyanate, an alicyclicisocyanate such as isophorone diisocyanate, an aromatic isocyanate suchas diphenylmethane isocyanate, a modified product thereof (e.g., atrimer of isophorone diisocyanate), and others.

[0243] The compound having an oxazoline group includes, for example, abisoxazoline compound such as 2,2′-(1,3-phenylene)-bis(2-oxazoline) and2,2′-(1,4-phenylene)-bis(2-oxazoline), a vinyl-series resin having anoxazoline group (e.g., a vinyl oxazoline-modified styrenic resin), andothers.

[0244] Examples of the compound having an oxazine group include abisoxazine compound such as 2,2′-bis(5,6-dihydro-4H-1,3-oxazine), andothers.

[0245] As the compound having a carbodiimide group, there may bementioned, for example, a polyarylcarbodiimide such as apoly(phenylcarbodiimide), and a poly(naphthylcarbodiimide); apolyalkylarylcarbodiimide such as a poly(2-methyldiphenylcarbodiimide),a poly(2,6-diethyldiphenylcarbodiimide), apoly(2,6-diisopropyldiphenylcarbodiimide), apoly(2,4,6-triisopropyldiphenylcarbodiimide), and apoly(2,4,6-tri-t-butyldiphenylcarbodiimide); a poly[alkylenebis(alkyl orcycloalkylaryl)carbodiimide] such as apoly[4,4′-methylenebis(2,6-diethylphenyl)carbodiimide], apoly[4,4′-methylenebis(2-ethyl-6-methylphenyl)carbodiimide], apoly[4,4′-methylenebis(2,6-diisopropylphenyl)carbodiimide], and apoly[4,4′-methylenebis(2-ethyl-6-methylcyclohexylphenyl)carbodiimide];and others.

[0246] These reactive stabilizers may be used singly or in combination.

[0247] The antioxidant (F) and/or stabilizer (G) may be used singly orin combination. The content of the antioxidant and/or stabilizer may forexample be selected within the range of about 0.01 to 5 parts by weight,preferably about 0. 05 to 3 parts by weight, and particularly about 0.1to 2 parts by weight, relative to 100 parts by weight of theflame-retardant resin composition.

[0248] Since the flame-retardant resin composition of the presentinvention comprises the inorganic filler (C), the composition isexcellent in dripping inhibition effects. Further, by the addition ofthe dripping inhibitor (H) such as a fluorine-containing resin, thecomposition may be improved in inhibition of effects on dripping ofkindling material and a molten solution upon combustion.

[0249] (H) Fluorine-Containing Resin

[0250] As the fluorine-containing resin (or fluorine-series resin) (H),there may be mentioned a homo- or copolymer of a fluorine-containingmonomer such as tetrafluoroethylene, chlorotrifluoroethylene, vinylidenefluoride, hexafluoropropylene and perfluoroalkyl vinyl ether; and acopolymer of the fluorine-containing monomer and a copolymerizablemonomer such as ethylene, propylene and acrylate. Examples of thefluorine-containing resin are a homopolymer such as apolytetrafluoroethylene, a polychlorotrifluoroethylene and apolyvinylidene fluoride; and a copolymer such as atetrafluoroethylene-hexafluoropropylene copolymer, atetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, anethylene-tetrafluoroethylene copolymer and anethylene-chlorotrifluoroethylene copolymer. These fluorine-containingresins may be used singly, or used as a mixture of not less than twospecies thereof.

[0251] The fluorine-containing resin (H) may be used in the form ofparticles, and the mean particle size may for example be about 10 to5,000 μm, preferably about 100 to 1,000 μm, and more preferably about100 to 700 μm.

[0252] The content of the fluorine-containing resin (H) is, for example,about 0.01 to 10 parts by weight, preferably about 0.1 to 5 parts byweight, and more preferably about 0.1 to 3 parts by weight, relative to100 parts by weight of the flame-retardant resin composition.

[0253] The antioxidant, the stabilizer, and the dripping inhibitor maybe used singly or in combination of two or more species. Theflame-retardant resin composition of the present invention preferablycomprises, in particular, at least one member selected from the hinderedphenol-series antioxidant, the phosphorus-containing stabilizer, theinorganic stabilizer, the reactive stabilizer, and thefluorine-containing resin among components mentioned above.

[0254] The flame retardant of the present invention imparts high flameretardancy to a resin probably because the flame retardant facilitatescarbonization of the resin surface on burning. Moreover, even in thecase using a halogen-free flame retardant including the polyphenyleneoxide-series resin, the combination use of the phosphoric ester and thepolyphosphate of the specific nitrogen-containing cyclic compoundeffectively realizes high flame retardancy of the base resin(particularly a polyester-series resin) in small amount of the flameretardant, and causes no possibility of bleeding out. In particular, theuse of the nitrogen-containing cyclic compound as a flame retardantcomponent considerably improves the flame retardant effects withoutcoloring or staining the resin composition.

[0255] Further, the flame-retardant resin composition of the presentinvention may comprise other additive(s) for any purpose. As otheradditive(s), there may be mentioned a stabilizer (e.g., an ultravioletray absorbing agent, a heat stabilizer, a weather (light) -resistantstabilizer), a lubricant, a mold-release agent (releasing agent), acoloring agent (colorant), a plasticizer,sa nucleating agent, an impactresistance improver (impact modifier), a slip-(friction/wear) improvingagent, a filler (e.g., an organic fiber having a high melting point,such an aliphatic or aromatic polyamide, an aromatic polyester, afluorocarbon resin, and an acrylic resin such as a polyacrylonitrile),and others.

[0256] The resin composition of the present invention may be aparticulate mixture or a molten mixture, and it may be prepared bymixing the base resin (e.g., a polyester-series resin such as apolyalkylene arylate-series resin) with the flame retardant, theinorganic filler, and if necessary, the additive(s), in a conventionalmanner.

[0257] The resin composition of the present invention may be formed bymelting and kneading, and molding with a conventional manner such asextrusion molding, injection molding and compression molding. Thusformed shaped article is excellent in flame retardancy and moldingprocessability (mold-processability), and may be utilized for variouspurposes. For example, the shaped article is suitable for an electric orelectronic device part, an office automation (OA) device part, ahousehold electrical appliance part, a mechanical device part, anautomotive part, and others.

Industrial Applicability

[0258] According to the present invention, the combination use of aspecific flame retardant, with an inorganic filler treated with anovolak epoxy resin inhibits dripping of a flame retardant resincomposition and a shaped article thereof. Moreover, the presentinvention provides a flame-retardant resin composition to which flameretardancy is imparted at a high level by using a halogen-free flameretardant without deteriorating properties of a polyester-series resin,and a shaped article formed with the composition.

EXAMPLES

[0259] The following examples are intended to describe this invention infurther detail and should by no means be interpreted as defining thescope of the invention. Incidentally, flame retardancy and bloomingproperties of a resin composition were evaluated on the basis of thefollowing tests.

[0260] (Flame Retardancy Test)

[0261] In accordance with UL94, the flame retardancy and drippingproperties were evaluated using a test piece 0.8 mm thick.

[0262] (Evaluation of Blooming Properties)

[0263] A test piece 0.8 mm thick for burning was heated at 150° C. for 5hours, and visually observed for the state of bleeding out in thesurface of the test piece. The blooming properties were evaluated on thebasis of the following judgmental standard.

[0264] “A”: no bleeding out was observed

[0265] “B”: slight bleeding out was observed

[0266] “C”: remarkable bleeding out was observed

[0267] [Base Resin A (Polyester-Series Resin A)]

[0268] A-1: Polybutylene terephthalate [“DURANEX”, intrinsic viscosity=1.0, manufactured by Polyplastics Co., Ltd.]

[0269] A-2: Polyethylene terephthalate [“BELLPET EFG”, manufactured byKanebo Gohsen, Ltd.]

[0270] [Flame Retardant B]

[0271] [Polyphenylene oxide-series resin, polyphenylene sulfide-seriesresin B1 (PPO/PPS B1)]

[0272] B1-1: Poly(2,6-dimethyl-1,4-phenylene)ether [“PPE polymerYPX-100F”, manufactured by Mitsubishi Gas Chemical Co., Inc.]

[0273] B1-2: Poly-1,4-phenylene-sulfide

[0274] [Phosphoric Ester B2]

[0275] B2-1: Resorcinol bis(di-2,6-xylyl phosphate) [“PX200”,manufactured by Daihachi Chemical Industry Co., Ltd.]

[0276] B2-2: Hydroquinonebis(di-2,6-xylylphosphate) [“PX201”,manufactured by Daihachi Chemical Industry Co., Ltd.]

[0277] B2-3: Biphenol bis(di-2,6-xylyl phosphate) [“PX202”, manufacturedby Daihachi Chemical Industry Co., Ltd.]

[0278] B2-4: Bisphenol-A bis(diphenyl phosphate) [“CR-741”, manufacturedby Daihachi Chemical Industry Co., Ltd.]

[0279] B2-5: N,N′-bis(di-2,6-xylyloxyphosphinyl)piperazine[1,4-piperazinediyltetra-2,6-xylyl phosphate]

[0280] B2-6: N,N′-bis(diphenoxyphosphinyl)piperazine[1,4-piperazinediyltetraphenyl phosphate]

[0281] B2-7: Cyclic phenoxyphosphazene

[0282] B2-8: N,N′-bis(neopentylenedioxyphosphinyl)piperazine[Nitrogen-containing cyclic compound B3]

[0283] B3-1: Melamine-melam-melem double salt of polyphosphoric acid[“PMP200”, manufactured by Nissan Chemical Industries, Ltd.]

[0284] B3-2: Polyphosphoric acid amide [“SUMISAFE PM”, manufactured bySumitomo Chemical Co., Ltd.]

[0285] B3-3: Melamine polyphosphate [“Melapur 200”, manufactured by DSM]

[0286] B3-4: Melamine polymetaphosphate: a compound synthesizedaccording to Example 1 described in Japanese Patent ApplicationLaid-Open No. 81691/1998 (JP-10-81691A)

[0287] B3-5: Melamine sulfate [“APINON 901”, manufactured by SanwaChemical Co., Ltd.]

[0288] B3-6: Melamine cyanurate [“MC610”, manufactured by NissanChemical Industries, Ltd.]

[0289] [Inorganic Filler C]

[0290] C-1: Glass chopped strand being 10 μm in diameter and 3 mm long,to which 1.2 wt % of a surface-treatment agent containing a novolakepoxy resin as a main component is bonded

[0291] C-2: Glass chopped strand being 13 μm in diameter and 3 mm long,to which 1.2 wt % of a surface-treatment agent containing a novolakepoxy resin as a main component is bonded

[0292] C-3: Glass chopped strand being 10 μm in diameter and 3 mm long,to which 1.2 wt % of a surface-treatment agent containing a bisphenolA-based epoxy resin as a main component is bonded

[0293] [Styrenic Resin D]

[0294] D-1: Polystyrene [“TOYO STYROL GP G200C”, manufactured by ToyoStyrene Co., Ltd.]

[0295] D-2: Acrylonitrile-styrene copolymer [“CEVIAN NJD”, manufacturedby Daicel Chemical Industries, Ltd.]

[0296] [Resinous Flame-Retardant Auxiliary E1]

[0297] E1-1: Polycarbonate [“PANLITE L1225”, manufactured by TeijinChemicals Ltd.]

[0298] E1-2: Phenoxy resin [“PHENOTOHTO YP-50”, manufactured by TohtoKasei Co., Ltd.]

[0299] E1-3: Novolak phenol resin [“SUMILITE RESIN PR-53647”,manufactured by Sumitomo Durez Co., Ltd.]

[0300] E1-4: Polyarylate [“POLYARYLATE U100”, manufactured by UnitikaLtd.]

[0301] E1-5: Bisphenol A-based epoxy resin [“EPIKOTE 828”, manufacturedby Yuka Shell Epoxy K.K.]

[0302] [Inorganic Flame-Retardant Auxiliary E2]

[0303] E2-1: Red phosphorus [“NOVA EXCEL 140”, manufactured by RinkagakuKogyo Co., Ltd.]

[0304] E2-2: Anhydrous calcium secondary phosphate [mean particle size=about 30 μm, manufactured by Taihei Chemical Industrial Co., Ltd.]

[0305] E2-3: Magnesium hydroxide [“KISUMA 5E”, manufactured by KyowaChemical Industry Co., Ltd.]

[0306] E2-4: Zinc borate [“FIREBRAKE ZB”, manufactured by Borax JapanLtd.]

[0307] E2-5: Magnesium hydroxide [Ni solid solution, “FINEMAG SN”,manufactured by TMG Corp.]

[0308] [Antioxidant F]

[0309] F-1:Pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate][“IRGANOX 1010”, manufactured by Ciba-Geigy Ltd.]

[0310] [Stabilizer G]

[0311] G-1: Bis-(2,6-di-t-butyl-4-methylphenyl) pentaerythritoldiphosphite [“ADK STAB PEP36”, manufactured by Adeka Argus Chemical Co.,Ltd.]

[0312] G-2: Tetrakis(2,4-di-t-butylphenyl)-4,4′-biphenylenediphosphonite [“SANDOSTAB P-EPQ”, manufactured by Sandoz.]

[0313] G-3: Hydrotalcite [“DHT-4A”, manufactured by Kyowa ChemicalIndustry Co., Ltd.]

[0314] G-4: Zeolite [“ZEOLAM A-3”, manufactured by Tosoh Corp.]

[0315] G-5: Glycidyl versatate

[0316] G-6: 1,4-bis([(3-ethyl-3-oxetanyl)methoxy]methyl}benzene

[0317] [Dripping Inhibitor H]

[0318] H-1: Polytetrafluoroethylene

Examples 1 to 45 and Comparative Examples 1 to 13

[0319] The above components were mixed in the ratio (parts by weight)described in Tables 1 to 4, and the mixture was kneaded and extrudedwith the use of an extruder to prepare a resin composition. The obtainedresin composition was subjected to injection molding to make a shapedarticle for flame retardancy test. The flame retardancy, drippingproperties and blooming properties were evaluated with the use of thetest shaped article. The results are shown in Tables 1 to 4. TABLE 1Examples 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 Polyester-seriesA-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1resin A (parts by weight) 100 100 100 100 100 100 100 100 100 100 100100 100 100 100 100 100 100 PPO/PPS B1 B1-1 B1-1 B1-1 B1-1 B1-1 B1-1B1-1 B1-1 B1-1 B1-1 B1-1 B1-1 B1-1 B1-1 B1-1 B1-1 B1-1 B1-1 (parts byweight) 30 50 30 30 30 30 30 50 40 40 40 40 40 40 50 40 40 40 Phosphoricester B2 B2-1 B2-1 B2-2 B2-3 B2-1 B2-1 B2-1 B2-1 B2-1 B2-2 B2-3 B2-1B2-1 B2-1 B2-1 B2-1 B2-4 B2-1 (parts by weight) 40 60 40 40 40 40 40 4040 40 40 40 40 40 40 40 40 15 Nitrogen-containing — — — — — — — B3-1B3-1 B3-1 B3-1 B3-2 B3-3 B3-4 B3-5 B3-1 B3-1 B3-1 cyclic compound B3(parts by weight) 15 15 15 15 15 15 15 15 15 15 40 Inorganic filler CC-1 C-1 C-1 C-1 C-1 C-1 C-2 C-1 C-1 C-1 C-1 C-1 C-2 C-1 C-1 C-1 C-2 C-1(parts by weight) 80 100 80 80 80 80 80 90 90 90 90 90 90 90 90 90 90 90Styrenic resin D D-1 D-1 D-1 D-1 D-2 D-1 D-2 — D-1 D-1 D-1 D-1 D-1 D-1D-1 D-1 D-2 D-1 (parts by weight) 10 15 10 10 10 10 10 10 10 10 10 10 1010 10 10 10 Resinous flame- — — — — — — — — — — — — — — — — — —retardant auxiliary E1 (parts by weight) Inorganic flame- — — — — — — —— — — — — — — — — — — retardant auxiliary E2 (parts by weight)Antioxidant F F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1F-1 F-1 F-1 F-1 (parts by weight) 0.8 1.0 0.8 0.8 0.8 0.8 0.8 1.0 1.01.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Stabilizer G — — — — — G-1 G-2 G-2 —— — G-3 G-2 G-4 G-5 G-1 G-2 G-2 (parts by weight) 0.8 0.8 1.0 — — — 3.01.0 3.0 3.0 1.0 1.0 1.0 Dripping inhibitor H H-1 H-1 H-1 H-1 H-1 H-1 H-1H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 (parts by weight) 1.3 1.51.3 1.3 1.3 1.3 1.3 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 UL94Flame V-1 V-0 V-1 V-1 V-1 V-1 V-1 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0V-0 V-0 Retardancy Dripping properties no no no no no no no no no no nono no no no no no no Blooming properties A A A A B A A A A A A A A A A AA A

[0320] TABLE 2 Examples 19 20 21 22 23 24 25 26 27 28 29 30 31 32Polyester-series A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1resin A 100 100 100 100 100 100 100 100 100 100 100 100 100 100 (partsby weight) PPO/PPS B1 B1-1 B1-1 B1-1 B1-1 B1-1 B1-1 B1-1 B1-1 B1-1 B1-1B1-1 B1-1 B1-1 B1-1 (parts by weight) 50 50 50 40 40 40 40 40 40 40 4040 40 40 Phosphoric ester B2 B2-1 B2-1 B2-1 B2-1 B2-1 B2-1 B2-1 B2-1B2-1 B2-1 B2-1 B2-1 B2-1 B2-1 (parts by weight) 60 60 60 40 40 40 40 4040 40 40 40 40 40 Nitrogen-containing — — — — — B3-1 B3-1 B3-1 B3-1 B3-1B3-1 B3-6 B3-1 B3-6 B3-1 cyclic compound B3 15 15 15 10 15 10  5 5 5 5(parts by weight) Inorganic filler C C-1 C-1 C-2 C-1 C-1 C-1 C-1 C-1 C-1C-1 C-1 C-1 C-1 C-1 (parts by weight) 100 100 100 80 90 90 90 90 90 9090 90 90 90 Styrenic resin D D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1D-1 D-1 D-1 (parts by weight) 15 15 15 10 10 10 10 10 10 10 10 10 10 10Resinous flame- E1-1 E1-2 E1-1 E1-2 E1-3 — E1-1 E1-2 E1-1 E1-2 E1-3 E1-4— — — — retardant auxiliary 3 3 3  3 3 3 3 3  3 3 3 E1 (parts by weight)Inorganic flame- E2-1 E2-1 — — E2-2 — E2-3 — — — — E2-2 E2-2 E2-4retardant auxiliary 3 3 15 3 5 5 5 E2 (parts by weight) Antioxidant FF-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 (parts byweight) 1.0 1.0 0.8 0.8 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0Stabilizer G G-1 — G-1 — — G-1 — G-1 — G-2 — — — — (parts by weight) 1.01.0 1.0 1.0 1.0 Dripping inhibitor H H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 —H-1 H-1 H-1 H-1 H-1 (parts by weight) 1.5 1.5 1.5 1.3 1.5 1.5 1.5 1.51.5 1.5 1.5 1.5 1.5 UL94 Flame V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0V-0 V-0 V-0 V-0 Retardancy Dripping properties no no no no no no no nono no no no no no Blooming properties A A A A A A A A A A A A A A

[0321] TABLE 3 Examples 33 34 35 36 37 38 39 40 41 42 43 44 45Polyester-series A-2 A-2 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-2 A-1 A-2 A-1A-2 A-1 A-2 resin A 100 100 100 100 100 100 100 100 100 70  30 50  5050  50 50  50 (parts by weight) PPO/PPS B1 B1-1 B1-1 B1-1 B1-2 B1-1 B1-2B1-1 B1-1 B1-1 B1-1 B1-1 B1-1 B1-1 B1-1 B1-1 (parts by weight) 30 2035  15 30  10 40 40 40 40 40 30 5 5 5 Phosphoric ester B2 B2-1 B2-1 B2-1B2-1 B2-5 B2-6 B2-7 B2-7 B2-8 B2-4 B2-1 B2-6 B2-7 (parts by weight) 4025 40 40 40 40 40 40 40 30 40 40 40 Nitrogen-containing — B3-1 B3-1 B3-1B3-1 B3-6 B3-1 B3-6 B3-1 B3-1 B3-1 B3-6 B3-6 B3-1 B3-6 cyclic compoundB3 12 15 15 15 15 15 15 15 10 15  50 65 15  50 (parts by weight)Inorganic filler C C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1(parts by weight) 80 70 90 90 90 90 90 90 90 80 100 100 100 Styrenicresin D D-1 D-1 — D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-2 D-2 D-2 (parts byweight) 10 8 10 10 10 10 10 10 10 15 15 15 Resinous flame-retardant — —— — — E1-5 — E1-1 E1-1 E1-5 E1-5 E1-5 E1-5 auxiliary E1 (parts by 3 3 33 3 3 3 weight) Inorganic flame-retardant — — — — — — — — — — — — —auxiliary E2 (parts by weight) Antioxidant F F-1 F-1 F-1 F-1 F-1 F-1 F-1F-1 F-1 F-1 F-1 F-1 F-1 (parts by weight) 0.8 0.8 1.0 1.0 1.0 1.0 1.01.0 1.0 1.0 1.0 1.0 1.0 Stabilizer G — — — — — G-3 — — — G-2 G-2 G-6 G-2G-2 (parts by weight) 3.0 1.0 1.0  3.0 1.0 1.0 Dripping inhibitor H H-1H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 (parts by weight) 1.31.3 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 UL94 Flame V-0 V-0 V-0V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Retardancy Dripping propertiesno no no no no no no no no no no no no Blooming properties A A A A A A AA A A A A A

[0322] TABLE 4 Comparative Examples 1 2 3 4 5 6 7 8 9 10 11 12 13Polyester-series resin A A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-2 A-1 A-1A-1 (parts by weight) 100 100 100 100 100 100 100 100 100 100 100 100100 PPO/PPS B1 B1-1 — B1-1 — B1-1 — B1-1 B1-1 B1-1 B1-1 B1-1 B1-1 B1-1(parts by weight) 30 30 30 30 40 40 20 40 40 40 Phosphoric ester B2 —B2-1 — B2-1 — B2-1 B2-1 B2-1 B2-1 B2-1 B2-5 B2-6 B2-7 (parts by weight)40 40 40 40 40 40 25 40 40 40 Nitrogen-containing — — — — — — — B3-6B3-5 B3-6 B3-6 B3-6 83-6 cyclic compound B3 15 15 12 15 15 15 (parts byweight) Inorganic filler C C-1 C-1 C-2 C-2 C-3 C-3 C-3 C-3 C-3 C-3 C-3C-3 C-3 (parts by weight) 80 80 80 80 80 80 80 90 90 70 90 90 90Styrenic resin D D-1 D-1 D-1 D-1 D-1 D-1 D-1 — D-1 — — — — (parts byweight) 10 10 10 10 10 10 10 10 Resinous flame-retardant — — — — — — — —— — — — — auxiliary E1 (parts by weight) Inorganic flame-retardant — — —— — — — — — — — — — auxiliary E2 (parts by weight) Antioxidant F F-1 F-1F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 (parts by weight) 0.8 0.80.8 0.8 0.8 0.8 0.8 1.0 1.0 0.8 1.0 1.0 1.0 Stabilizer G — — — — — — — —— — — — — (parts by weight) Dripping inhibitor H H-1 H-1 H-1 H-1 H-1 H-1H-1 H-1 H-1 H-1 H-1 H-1 H-1 (parts by weight) 1.3 1.3 1.3 1.3 1.3 1.31.3 1.5 1.5 1.3 1.5 1.5 1.5 U194 Flame Retardancy HB HB HB HB HB HB V-2V-1 V-1 V-1 V-1 V-1 V-1 Dripping properties yes yes yes yes yes yes yesyes yes yes yes yes yes Blooming properties A C A C A C A A A A A A A

1. A flame-retardant resin composition, which comprises a base resin(A), a flame retardant (B) and an inorganic filler (C), wherein theflame retardant comprises (B1) at least one member selected from thegroup consisting of a polyphenylene oxide-series resin and apolyphenylene sulfide-series resin, and (B2) a phosphoric ester, andwherein (B3) a nitrogen containing cyclic compound, and the inorganicfiller (C) has been treated with a surface-treatment agent or sizingagent containing a novolak epoxy resin.
 2. A flame-retardant resincomposition according to claim 1, wherein the inorganic filler (C)comprises at least one member selected from the group consisting of aglass fiber and a glass flake.
 3. A flame-retardant resin compositionaccording to claim 1, wherein the amount of the surface-treatment agentor sizing agent is 0.01 to 5 parts by weight relative to 100 parts byweight of the inorganic filler.
 4. A flame-retardant resin compositionaccording to claim 1, which further comprises a styrenic resin (D).
 5. Aflame-retardant resin composition according to claim 1, wherein the baseresin (A) comprises at least one thermoplastic resin selected from thegroup consisting of a polyester-series resin, a polyamide-series resin,an olefinic resin, an acrylic resin, and a vinyl-series resin.
 6. Aflame-retardant resin composition according to claim 1, wherein the baseresin (A) comprises a homo- or co-polyester having at least one unitselected from the group consisting of 1,4-cyclohexanedimethyleneterephthalate, a C2-4alkylene terephthalate, and a C2-4 alkylenenaphthalate.
 7. (cancelled)
 8. A flame-retardant resin compositionaccording to claim 1, wherein the proportions of the flame retardant (B)and the inorganic filler (C) are 10 to 300 parts by weight and 1 to 200parts by weight, respectively, relative to 100 parts by weight of thebase resin (A).
 9. A flame-retardant resin composition according toclaim 1, wherein the flame retardant (B) comprises 10 to 500 parts byweight of the component (B1) and 0 to 1000 parts by weight of thenitrogen-containing cyclic compound (B3), relative to 100 parts byweight of the phosphoric ester (B2).
 10. A flame-retardant resincomposition, which comprises: at least one base resin (A) selected fromthe group consisting of a polybutylene terephthalate, a copolyestercontaining a butylene terephthalate as a main unit thereof, apolyethylene terephthalate, and a copolyester containing an ethyleneterephthalate as a main unit thereof, a flame retardant (B), and a glassfiber (C); wherein the flame retardant (B) comprises the followingcomponents (B1) and (B2): (B1) at least one member selected from thegroup consisting of a polyphenylene oxide-series resin and apolyphenylene sulfide-series resin, and (B2) a condensed phosphoricester; and wherein the surface of the glass fiber (C) has been treatedwith 0.05 to 3 parts by weight of a surface-treatment agent or sizingagent containing a novolak epoxy resin relative to 100 parts by weightof the glass fiber.
 11. A flame-retardant resin composition according toclaim 1, which further comprises at least one flame-retardant auxiliaryselected from the group consisting of a resinous flame-retardantauxiliary (E1), and an inorganic flame-retardant auxiliary (E2).
 12. Aflame-retardant resin composition according to claim 11, wherein theresinous flame-retardant auxiliary (E1) comprises at least one aromaticresin selected from the group consisting of a resin of which the mainchain or side chain contains an aromatic ring having at least one groupselected from a hydroxyl group and an amino group, a polyarylate-seriesresin, an aromatic epoxy resin, and a polycarbonate-series resin; andthe inorganic flame-retardant auxiliary (E2) comprises at least onemember selected from the group consisting of a metal borate, a metalhydrogenphosphate, a metal oxide, a metal hydroxide, a metal sulfide,and a red phosphorus.
 13. A flame-retardant resin composition accordingto claim 1, which further comprises at least one additive selected fromthe group consisting of a fluorine-containing resin, a hinderedphenol-series antioxidant, a phosphorus-containing stabilizer, aninorganic stabilizer, and a compound having a functional group reactiveto an active hydrogen atom.
 14. A shaped article formed with aflame-retardant resin composition recited in claim
 1. 15. A shapedarticle according to claim 14, which is an electric or electronic devicepart, an office automation device part, a household electrical appliancepart, an automotive part, or a mechanical part or machine element.
 16. Aflame-retardant resin composition according to claim 1, wherein theflame retardant (B) comprises (B1) at least one member selected from thegroup consisting of a polyphenylene oxide-series resin and apolyphenylene sulfide-series resin, (B2) a phosphoric ester, and (B3) anitrogen-containing cyclic compound.
 17. A flame-retardant resincomposition according to claim 16, wherein the phosphoric ester (B2)comprises a condensed phosphoric ester, and the nitrogen-containingcyclic compound (B3) comprises at least one member selected from thegroup consisting of a polyphosphate of an amino group-containingtriazine compound, and a polyphosphoric acid amide.
 18. Aflame-retardant resin composition according to claim 16, wherein theproportion of the nitrogen-containing cyclic compound (B3) is 12.5 to1000 parts by weight, relative to 100 parts by weight of the phosphoricester (B2).
 19. A flame-retardant resin composition according to claim10, wherein the flame retardant (B) comprises the following components(B1), (B2), and (B3): (B1) at least one member selected from the groupconsisting of a polyphenylene oxide-series resin and a polyphenylenesulfide-series resin, (B2) a condensed phosphoric ester, and (B3) a saltof a polyphosphoric acid having a condensation degree of 3 to 200 withat least one member selected from the group consisting of melamine and amelamine condensate.